2-benzoyl-cyclohexane-1,3-diones

ABSTRACT

Substituted 2-benzoylcyclohexane-1,3-diones of the formula I                    
     where: 
     R 1  and R 2  are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, —OR 3 , —OCOR 3 , —OSO 2 R 3 , —S(O) n R 3 , —SO 2 OR 3 , —SO 2 N(R 3 ) 2 , —NR 3 SO 2 R 3  or —NR 3 COR 3 ; 
     R 3  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, phenyl or phenyl-C 1 -C 6 -alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups: 
     hydroxyl, mercapto, amino, cyano, R 3 , —OR 3 , —SR 3 , —N(R 3 ) 2 , ═NOR 3 , —OCOR 3 , —SCOR 3 , —NR 3 COR 3 , —CO 2 R 3 , —COSR 3 , —CON(R 3 ) 2 , C 1 -C 4 -alkyliminooxy, C 1 -C 4 -alkoxyamino, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxy-C 2 -C 6 -alkoxycarbonyl, C 1 -C 4 -alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted; 
     n is 0, 1 or 2; 
     Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2; 
     X 1  is a straight-chain or branched C 1 -C 6 -alkylene, a C 2 -C 6 -alkenylene or a C 2 -C 6 -alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups: 
     —OR 4 , —OCOR 4 , —OCONHR 4  or —OSO 2 R 4 ; 
     except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position; 
     R 4  is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, phenyl, phenyl-C 1 -C 6 -alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals: 
     hydroxyl, mercapto, amino, cyano, nitro, formyl, C 1 -C 4 -alkylamino, C 1 -C 4 -dialkylamino, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkylcarbonyloxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy; 
     Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of: 
     nitrogen, oxygen or sulfur, 
     where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R 5 ; 
     R 5  is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C 1 -C 4 -alkylamino, C 1 -C 4 -dialkylamino, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkylcarbonyloxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals: 
     cyano, formyl, C 1 -C 4 -alkylamino, C 1 -C 4 -dialkylamino, C 1 -C 4 -alkoxycarbonyl, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkylcarbonyloxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy; 
     and agriculturally useful salts thereof, processes and intermediates for preparing compounds of the formula I, compositions comprising them, and the use of the compounds of the formula I and compositions comprising them for controlling harmful plants are described.

The present invention relates to substituted 2-benzoylcyclohexane-1,3-diones of the formula I

where:

R¹ and R² are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR³, —OCOR³, —OSO₂R³, —S(O)_(n)R³, —SO₂OR³, —SO₂N(R³)₂, —NR³SO₂R³ or —NR³COR³;

R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl or phenyl-C₁-C₆-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:

hydroxyl, mercapto, amino, cyano, R³, —OR³, —SR³, —N(R³)₂, ═NOR³, —OCOR³, —SCOR³, —NR³COR³, —CO₂R³, —COSR³, —CON(R³)₂, C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;

n is 0, 1 or 2;

Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2;

X¹ is a straight-chain or branched C₁-C₆-alkylene, a C₂-C₆-alkenylene or a C₂-C₆-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:

—OR⁴, —OCOR⁴, —OCONHR⁴ or —OSO₂R⁴;

except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;

R⁴ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl, phenyl-C₁-C₆-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals:

hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:

nitrogen, oxygen and sulfur,

where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵;

R⁵ is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:

cyano, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

and agriculturally useful salts thereof.

In addition, the invention relates to processes and intermediates for preparing compounds of the formula I, to compositions comprising them and to the use of the compounds of the formula I and to compositions comprising them for controlling harmful plants.

2-Benzoylcyclohexane-1,3-diones are disclosed in the literature, for example in EP-A 278 742, EP-A 298 680, EP-A 320 864 and is WO 96/14285.

However, the herbicidal properties of the prior art compounds and their crop plant safety are not entirely satisfactory.

It is an object of the present invention to provide novel, in particular herbicidally active, compounds having improved properties.

We have found that this object is achieved by the 2-benzoylcyclohexane-1,3-diones of the formula I and their herbicidal activity.

Furthermore, we have found herbicidal compositions which comprise the compounds I and have very good herbicidal activity. Moreover, we have found processes for preparing these compositions and methods for controlling unwanted vegetation using the compounds I.

The present invention also provides stereoisomers of the compounds of the formula I. Pure stereoisomers and also mixtures thereof are included.

Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers and, if this is the case, are present as mixtures of enantiomers or diastereomers. The invention provides the pure enantiomers or diastereomers and also mixtures thereof.

The compounds of the formula I may also be present in the form of their agriculturally useful salts, the kind of salt generally not being important. The salts of those cations or the acid addition salts of those acids whose cations or anions, respectively, do not adversely affect the herbicidal activity of the compounds I are generally suitable.

Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium, where, if desired, one to four hydrogen atoms may be replaced by C₁-C₄-alkyl or hydroxy-C₁-C₄-alkyl and/or one phenyl or benzyl, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C₁C₄-alkyl)sulfoxonium.

Anions of usable acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate.

Emphasis is given to the compounds of the formula I according to the invention where the variable Q is a cyclohexane-1,3-dione ring of the formula II

which is attached in position 2, where II may also represent the tautomeric formulae II′ and II″,

where

R⁶, R⁷, R⁹ and R¹¹ are each hydrogen or C₁-C₄-alkyl;

R⁸ is hydrogen, C₁-C₄-alkyl or C₃-C₄-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents:

halogen, C₁-C₄-alkylthio or C₁-C₄-alkoxy; or

is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3ioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where the 6 last mentioned radicals may be substituted by one to three C₁-C₄-alkyl radicals;

R¹⁰ is hydrogen, C₁-C₄-alkyl or C₁-C₆-alkoxycarbonyl; or

R⁸ and R¹¹ together form a a bond or a three- to six-membered carbocyclic ring; or

the CR⁸R⁹ unit may be replaced by C═O.

Process A:

Reactions of the cyclohexane-1,3-dione of the formula II with an activated carboxylic acid IIIa or a carboxylic acid IIIb, which is preferably activated in situ, to give the acylation product IV, and subsequent rearrangement to the compounds of the formula I according to the invention

L¹ is a nucleophilically replaceable leaving group such as halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, or carboxylate, for example acetate, trifluoroacetate, etc.

The activated carboxylic acid can be employed directly, as in the case of acyl halides, or be generated in situ, for example by using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic esters, 2-pyridine disulfite/triphenylphosphine, carbonyldiimidazole, etc.

It may be advantageous to carry out the acylation reaction in the presence of a base. Starting materials and auxiliary base are advantageously employed in equimolar amounts. A slight excess of auxiliary base, for example 1.R to 1.5 molar equivalents, based on II, may be advantageous under certain circumstances.

Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Examples of solvents which can be used are chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene, chlorobenzene, ethers, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters such as ethyl acetate or mixtures of these.

If acyl halides are employed as activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10° C. when adding this reaction partner. The mixture is subsequently stirred at 20-100° C., preferably at 25-50° C., until the reaction is complete. Work-up is carried out in a customary manner, for example by pouring the reaction mixture into water and extracting the product of value. Solvents which are particularly suitable for this purpose are methylene chloride, diethyl ether and ethyl acetate. After the organic phase has been dried and the solvent has been removed, the crude enol ester of the formula IV is purified, preferably by chromatography. Alternatively, it is possible to employ the crude enol ester of the formula IV without further purification for the rearrangement reaction.

The rearrangement of the enol esters of the formula IV to the compounds of the formula I is advantageously carried out at from 20 to 40° C. in a solvent and in the presence of a base and, if appropriate, in the presence of a cyano compound.

Examples of solvents which can be used are acetonitrile, methylene chloride, 1,2-dichloroethane, dioxane, ethyl acetate, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.

Suitable bases are tertiary amines such as triethylamine, pyridine or alkali metal carbonates such as sodium carbonate, potassium carbonate, which are preferably employed in equimolar amounts or up to a four-fold excess, based on the ester. Preference is given to using triethylamine or alkali metal carbonates.

Suitable cyano compounds are inorganic cyanides such as sodium cyanide, potassium cyanide and organic cyano compounds such as acetone cyanohydrin, trimethylsilyl cyanide. They are employed in an amount of 1 to 50 mol percent, based on the ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of 5 to 15, preferably 10, mol percent, based on the ester.

Particular preference is given to employing alkali metal carbonates, such as potassium carbonate, in acetonitrile or dioxane.

Work-up can be carried out in a manner known per se. For example, the reaction mixture is acidified with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride, ethyl acetate. The organic phase can be extracted with 5-10% strength alkali metal carbonate solution, for example sodium carbonate or potassium carbonate solution. The aqueous phase is acidified, and the precipitate which forms is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated.

(Examples of the synthesis of esters of hydroxypyrazoles and the rearrangement of the esters are mentioned for example in EP-A 282 944 or U.S. Pat. No. 4,643,757).

The benzoic acids of the formula III are novel,

where:

R¹ and R² are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR³, —OCOR³, —OSO₂R³, —S(O)_(n)R³, —SO₂OR³, —SO₂N(R³)₂, —NR³SO₂R³ or —NR³COR³;

R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl or phenyl-C₁-C₆-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:

hydroxyl, mercapto, amino, cyano, R³, —OR³, —SR³, —N(R³)₂, ═NOR³, —OCOR³, —SCOR³, —NR³COR³, —CO₂R³, —COSR³, —CON(R³)₂, C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;

n is 0, 1 or 2;

X¹ is a straight-chain or branched C₁-C₆-alkylene, a C₂-C₆-alkenylene or a C₂-C₆-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:

—OR⁴, —OCOR⁴, —OCONHR⁴ or —OSO₂R⁴;

except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;

R⁴ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl, phenyl-C₁-C₆-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals:

hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:

nitrogen, oxygen and sulfur,

where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵;

R⁵ is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:

cyano, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy;

R¹² is hydroxyl or a hydrolyzable radical.

Examples of hydrolyzable radicals are alkoxy, phenoxy, alkylthio and phenylthio radicals which possibly are substituted, halides, hetaryl radicals which are bonded via nitrogen, amino and imino radicals which possibly are substituted, etc.

Preference is given to benzoyl halides IIIa where L¹=halogen ({circumflex over (=)} III where R¹²=halogen),

where the variables R¹, R², X¹ and Het are each as defined under formula III and

L¹ is halogen, in particular chlorine or bromine.

Preference is also given to benzoic acids of the formula IIIb ({circumflex over (=)} III where R¹²=hydroxyl),

where the variables R¹, R², X¹ and Het are each as defined under formula III.

Preference is also given to benzoic esters of the formula IIIc ({circumflex over (=)} III where R¹²=C₁-C₆-alkoxy),

where the variables R¹, R², X¹ and Het are each as defined under formula III and

M is C₁-C₆-alkoxy.

The compounds of the formula IIIa (where L¹=halogen) can be synthesized by methods similar to those known from the literature (cf. L.G. Fieser, M. Fieser “Reagents for Organic Synthesis”, Vol. I, pp. 767-769 (1967)) by reacting benzoic acids of the formula IIIb with halogenating agents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.

The benzoic acids of the formula IIIb can be obtained, inter alia, by hydrolyzing the benzoic esters of the formula IIIc (where M=C₁-C₆-alkoxy).

The benzoic esters of the formula IIIc according to the invention are preparable by various methods known from the literature (for example a: G. Dittus in Houben-Weyl, Methoden der Organischen Chemie, Volume VI/3, Oxygen compounds I, 4th edition, p. 493 ff., Georg Thieme Verlag, 1965; b: T. L. Gilchrist, Heterocyclenchemie, 2nd edition, Verlag Chemie, 1995) as illustrated in the examples that follow.

Process B:

Metallation of appropriate benzoic esters IIIc ortho to the ester function using strong organometallic bases and subsequent 1,2-addition of a carbonyl compound V yields the benzoic esters IIIe according to the invention,

where R¹³ is a substituent R¹ suitable for ortho-metallation (for example V. Snieckus, Chem. Rev. 90, (1990), 879), preferably halogen and C₁-C₆-alkoxy, and

X² is a straight-chain or branched C₁-C₅-alkylene, a C₂-C₅-alkenylene or a C₂-C₅-alkynylene chain where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:

—OR⁴, —OCOR⁴, —OCONHR⁴ or —OSO₂R⁴,

except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position.

Suitable organometallic bases for ortho-metallation of the benzoic esters IIId, which are known from the literature, include, for example, alkyllithium compounds, preferably n-butyllithium or sec-butyllithium, lithium dialkylamides, preferably lithium diisopropylamide or sodium hexamethyldisilazide.

Suitable inert solvents for the direct ortho-metallation are, for example, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane or 1,4-dioxane, dimethylformamide, dimethyl sulfoxide, methyl tert-butyl ether, or else mixtures of these.

The reaction temperatures can be from −80 to 100° C., preferably from −80 to 40° C.

The reaction of the ortho-metallated benzoic esters IIId, generated in situ, with the aldehydes V is carried out at reaction temperatures of from −80 to 100° C.

The products IIIe according to the invention contain a hydroxymethylene group which is suitable for further derivatizations by methods known from the literature. Thus, the hydroxymethylene group can for example be methylated to give the methoxy group.

Process C:

1,3-Dipolar cycloaddition of the benzoic esters IIIg with substituted or unsubstituted olefins or acetylenes under dehydrating conditions gives the benzoic esters according to the invention such as, for example, IIIh.

For dehydration by the method of Mukaiyama, preference is given to employing aromatic isocyanates (for example T. Mukaiyama et al., J. Am. Chem. Soc. 82 (1960) 5339), for example phenyl isocyanate or 4-chlorophenyl isocyanate.

For the Shimizu variant, aliphatic chloroformates (for example T. Shimizu et al., Bull. Chem. Soc. Jpn. 59 (1986), 2827), preferably ethyl chloroformate, are also suitable.

More recent developments show that it is also possible to employ for example N,N-diethylaminosulfur trifluoride (DAST), (methoxycarbonylsulfamoyl) triethylammonium hydroxide (Burgess reagent), phosphoryl chloride (for example C. Mioskowski et al., Tetrahedron Letters 38 (1997) 1547) or else a combination of di-tert-butyl dicarbonate (Boc₂O) and 4-dimethylaminopyridine (DMAP) (A. Hassner et al., Synthesis 1997, 309) successfully as dehydrating agents for generating nitrile oxides.

At room temperature up to the boiling point of the solvent employed, the nitrile oxides generated in situ in this manner can be reacted with acetylenes or olefins having any desired substitution to give the benzoic esters hIIc according to the invention, X¹ here being for example a methylene group and Het an isoxazoline or isoxazole skeleton with or without substitution.

The cycloaddition is carried out in inert solvents such as, for example, toluene, chloroform or acetonitrile.

The benzoic ester IIIg can be obtained from IIIj by reduction according to methods known from the literature, IIIj being obtainable by nitroolefination (for example a: V. V. Perekalin et al., Nitroalkenes, John Wiley & Sons Ltd., New York 1994, b: A. G. M. Barrett et al., Chem. Rev. 86 (1986), 751) of the corresponding aldehyde IIIi.

Emphasis is given to the compounds of the formula I according to the invention where the group X¹ is either a C₁-C₂-alkylene or a C₂-alkenylene chain and

Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:

nitrogen, oxygen and sulfur,

where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵.

Additionally, emphasis is given to the compounds of the formula I according to the invention where the group Het is a five- or six-membered partially or fully saturated heterocyclic or a five- or six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵;

R⁵ is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals:

cyano, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy.

The organic moieties mentioned for the substituents R¹-R¹³ or as radicals on phenyl, hetaryl and heterocyclyl rings are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, ie. all alkyl, haloalkyl, cycloalkyl, alkoxyalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkoxyamino, alkylsulfonyl, haloalkylsulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkoxyalkoxycarbonyl, alkenyl, cycloalkenyl, alkynyl moieties can be straight-chain or branched. Unless otherwise specified, halogenated substituents preferably carry one to five identical or different halogen atoms, the meaning of halogen being in each case fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

C₁-C₄-alkyl and the alkyl moieties of C₁-C₄-alkylcarbonyl: methyl, ethyl, n-propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;

C₁-C₆-alkyl and the alkyl moieties of C₁-C₆-alkoxy-C₁-C₆-alkyl and C₁-C₆-alkylcarbonyl: C₁-C₄-alkyl as mentioned above, and also pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;

C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;

C₁-C₆-haloalkyl and the haloalkyl moieties of C₁-C₆-haloalkylcarbonyl: C₁-C₄-haloalkyl as mentioned above, and also 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;

C₁-C₄-alkoxy and the alkoxy moieties of C₁-C₄-alkoxyamino, C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl and C₁-C₄-alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy; C₁-C₆-alkoxy and the alkoxy moieties of C₁-C₆-alkoxy-C₁-C₆-alkyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl and C₁-C₆-alkoxycarbonyl: C₁-C₄-alkoxy as mentioned above, and also pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;

C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, eg. fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;

C₁-C₄-alkylsulfonyl (C₁-C₄-alkyl-S(═O)₂—): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;

C₁-C₆-alkylsulfonyl: C₁-C₄-alkylsulfonyl as mentioned above, and also pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;

C₁-C₆-haloalkylsulfonyl: a C₁-C₆-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl and dodecafluorohexylsulfonyl;

C₁-C₄-alkyliminooxy: methyliminooxy, ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy, 1-butyliminooxy and 2-butyliminooxy;

C₃-C₆-alkenyl: prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;

C₂-C₆-alkenyl: C₃-C₆-alkenyl as mentioned above, and also ethenyl;

C₃-C₆-alkynyl: prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl;

C₂-C₆-alkynyl: C₃-C₆-alkynyl as mentioned above, and also ethynyl:

C₃-C₆-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

C₄-C₆-cycloalkenyl: cyclobuten-1-yl, cyclobuten-3-yl, cyclopenten-1-yl, cyclopenten-3-yl, cyclopenten-4-yl, cyclohexen-1-yl, cyclohexen-3-yl and cyclohexen-4-yl;

heterocyclyl, and also the heterocyclyl radicals in heterocyclyloxy: three- to seven-membered saturated or partially unsaturated mono- or polycyclic heterocycles which contain one to three hetero atoms selected from a group consisting of oxygen, nitrogen and sulfur, such as oxiranyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl, 1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,3-dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl, 2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl, 2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl, 2,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazol-5-yl, 2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl, 2,5-dihydropyrazol-4-yl, 2,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl, 2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl, 2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl, 4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl, 4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl, 2,5-dihydroimidazol-4-yl, 2,5-dihydroimidazol-5-yl, 2-morpholinyl, 3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl, 3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-3,1-benzothiazin-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazin-3-yl, 2H-1,4-benzoxazin-3-yl, 1,3-dihydrooxazin-2-yl,

hetaryl, and also the hetaryl radicals in hetaryloxy: aromatic mono- or polycyclic radicals which, besides carbon ring members, may additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen and one sulfur atom, eg. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4,5-tetrazin-3-yl, and also the corresponding benzo-fused derivatives.

All phenyl, hetaryl and heterocyclyl rings are preferably unsubstituted or carry one to three halogen atoms and/or one or two radicals selected from the following group: nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy or methoxycarbonyl.

With a view to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the following meanings, viz. in each case alone or in combination:

R¹ is nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR³ or —S(O)_(n)R³;

particularly preferably nitro, halogen such as, for example, fluorine, chlorine or bromine, C₁-C₆-haloalkyl, —OR³ or —SO₂R³;

R² is hydrogen, nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR³ or —S(O)_(n)R³;

particularly preferably hydrogen, nitro, halogen such as, for example, fluorine, chlorine or bromine, C₁-C₆-alkyl, C₁-C₆-haloalkyl, —OR³ or —SO₂R³;

R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl or phenyl-C₁-C₆-alkyl;

particularly preferably hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₂-C₃-alkenyl, C₂-C₃-alkynyl or phenyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups:

hydroxyl, mercapto, amino, cyano, R³, —OR³, —SR³, —N(R³)₂, ═NOR³, —OCOR³, —SCOR³, —NR³COR³, —CO₂R³, —COSR³, —CON(R³)₂, C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted;

n is 0, 1 or 2, particularly preferably 0 or 2;

X¹ is a straight-chain or branched C₁-C₄-alkylene, a propylene or butenylene or a C₂-C₄-alkynylene chain, particularly preferably a methylene, ethylene, propylene, propenylene, ethynylene or propynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups:

—OR⁴, —OCOR⁴, —OCONHR⁴ or —OSO₂R⁴;

except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position;

R⁴ is hydrogen, C₁-C₆-alkyl or C₁-C₆-haloalkyl; particularly preferably hydrogen, methyl, ethyl or trifluoromethyl;

R⁵ is C₁-C₆-alkyl or C₁-C₆-haloalkyl; particularly preferably methyl, ethyl, propyl, isopropyl, butyl or isobutyl;

R⁶, R⁷, R⁹ and R¹¹ are each hydrogen or C₁-C₄-alkyl;

particularly preferably hydrogen, methyl or ethyl;

R⁸ is hydrogen, C₁-C₄-alkyl, C₃-C₄-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents: halogen, C₁-C₄-alkoxy or C₁-C₄-alkylthio;

or is tetrahydropyran2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolant2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithian-2-yl or 1,3-dithiolan-2-yl, where the six last mentioned groups may in each case carry one to three C₁-C₄-alkyl radicals;

particularly preferably hydrogen, methyl, ethyl, cyclopropyl, di(methoxy)methyl, di(ethoxy)methyl, 2-ethylthiopropyl, tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 5,5-dimethyl-1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl or 1-methylthiocyclopropyl; R¹⁰ is hydrogen, C₁-C₄-alkyl or C₁-C₄-alkoxycarbonyl;

particularly preferably hydrogen, methyl or methoxycarbonyl.

Likewise, it may be advantageous for R⁸ and R¹¹ to form a π bond, thus giving rise to a double bond system.

Alternatively, the CR⁸R⁹ unit may be replaced by C═O.

Particular preference is given to the compounds of the formula Ia, where R¹ is attached in position 2 and R² is attached in position 4 of the phenyl ring.

Most particular preference is given to the compounds of the formula Ia in which the substituents R¹, R² and Q are each as defined above, X¹ is a C₁-C₂-alkylene or a C₂-alkynylene chain and

Het is a three- to six-membered, partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:

nitrogen, oxygen and sulfur,

where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵.

Particular preference is given to the compounds of the formula Ia where R¹ is attached in position 2 and R² is attached in position 4 of the phenyl ring.

Very particular preference is given to the compounds of the formula Ia in which the substituents R¹, R² und Q are each as defined above, X¹ is a C₁-C₂-alkylene or a C₂-alkynylene chain and

Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of:

nitrogen, oxygen and sulfur,

where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵.

Furthermore, very particular preference is given to the compounds of the formula Ia according to the invention in which the substituents R¹, R² and X¹ are each as defined above and Het is a five- or six-membered partially or fully saturated heterocyclic or a five- or six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of

nitrogen, oxygen and sulfur.

Particular preference is given to the compounds Ib of Tables 1 to 36.

TABLE A No. X¹ Het 1 CH₂ oxiranyl 2 CH₂ 3-methyl-2-oxiranyl 3 CH₂ 2-oxetanyl 4 CH₂ 3-hydroxy-3-methyl-2-oxetanyl 5 CH₂ 3-hydroxy-3-ethyl-2-oxetanyl 6 CH₂ 3-hydroxy-3-propyl-2-oxetanyl 7 CH₂ 3-hydroxy-3-butyl-2-oxetanyl 8 CH₂ 3-methoxy-3-methyl-2-oxetanyl 9 CH₂ 3-methoxy-3-ethyl-2-oxetanyl 10 CH₂ 3-methoxy-3-propyl-2-oxetanyl 11 CH₂ 3-methoxy-3-butyl-2-oxetanyl 12 CH₂ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 13 CH₂ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 14 CH₂ 3-trimethylsilyloxy-3-propyl-2-oxetanyl 15 CH₂ 3-trimethylsilyloxy-3-butyl-2-oxetanyl 16 CH₂ 3-oxetanyl 17 CH₂ 2-furyl 18 CH₂ 4,5-dihydro-2-furyl 19 CH₂ 2,3-dihydro-2-furyl 20 CH₂ 3-furyl 21 CH₂ 4,5-dihydro-3-furyl 22 CH₂ 2,3-dihydro-3-furyl 23 CH₂ 2-thienyl 24 CH₂ 4,5-dihydro-2-thienyl 25 CH₂ 2,3-dihydro-2-thienyl 26 CH₂ 5-chloro-2-thienyl 27 CH₂ 5-methyl-2-thienyl 28 CH₂ 3-thienyl 29 CH₂ 4,5-dihydro-3-thienyl 30 CH₂ 2,3-dihydro-3-thienyl 31 CH₂ 2-pyrrolyl 32 CH₂ 2,5-dihydro-2-pyrrolyl 33 CH₂ 3-pyrrolyl 34 CH₂ 2,5-dihydro-3-pyrrolyl 35 CH₂ 3-isoxazolyl 36 CH₂ 4-methyl-3-isoxazolyl 37 CH₂ 5-methyl-3-isoxazolyl 38 CH₂ 4,5-dimethyl-3-isoxazolyl 39 CH₂ 4,5-dihydro-3-isoxazolyl 40 CH₂ 4-methyl-4,5-dihydro-3-isoxazolyl 41 CH₂ 5-methyl-4,5-dihydro-3-isoxazolyl 42 CH₂ 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 43 CH₂ 4-isoxazolyl 44 CH₂ 3-methyl-4-isoxazolyl 45 CH₂ 5-methyl-4-isoxazolyl 46 CH₂ 5-cyclopropyl-4-isoxazolyl 47 CH₂ 5-phenyl-4-isoxazolyl 48 CH₂ 3,5-dimethyl-4-isoxazolyl 49 CH₂ 4,5-dihydro-4-isoxazolyl 50 CH₂ 3-methyl-4,5-dihydro-4-isoxazolyl 51 CH₂ 5-methyl-4,5-dihydro-4-isoxazolyl 52 CH₂ 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 53 CH₂ 5-isoxazolyl 54 CH₂ 3-methyl-5-isoxazolyl 55 CH₂ 4-methyl-5-isoxazolyl 56 CH₂ 3,4-dimethyl-5-isoxazolyl 57 CH₂ 4,5-dihydro-5-isoxazolyl 58 CH₂ 3-methyl-4,5-dihydro-5-isoxazolyl 59 CH₂ 4-methyl-4,5-dihydro-5-isoxazolyl 60 CH₂ 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 61 CH₂ 3-isothiazolyl 62 CH₂ 4-methyl-3-isothiazolyl 63 CH₂ 5-methyl-3-isothiazolyl 64 CH₂ 4-isothiazolyl 65 CH₂ 3-methyl-4-isothiazolyl 66 CH₂ 5-methyl-4-isothiazolyl 67 CH₂ 5-isothiazolyl 68 CH₂ 3-methyl-5-isothiazolyl 69 CH₂ 4-methyl-5-isothiazolyl 70 CH₂ 2-oxazolyl 71 CH₂ 4-oxazolyl 72 CH₂ 5-oxazolyl 73 CH₂ 2-thiazolyl 74 CH₂ 4-thiazolyl 75 CH₂ 5-thiazolyl 76 CH₂ 3-pyrazolyl 77 CH₂ 4-pyrazolyl 78 CH₂ 1-methyl-3-pyrazolyl 79 CH₂ 1-methyl-4-pyrazolyl 80 CH₂ 1-methyl-5-pyrazolyl 81 CH₂ 2-imidazolyl 82 CH₂ 1-methyl-2-imidazolyl 83 CH₂ 5-methyl-[1,3,4]-2-oxadiazolyl 84 CH₂ 5-methyl-[1,2,4]-3-oxadiazolyl 85 CH₂ 5-methyl-[1,3,4]-2-thiadiazolyl 86 CH₂ 5 methyl-[1,2,4]-3-thiadiazolyl 87 CH₂ [1,2,4]-3-triazolyl 88 CH₂ [1,2,3]-4-triazolyl 89 CH₂ 2-pyridyl 90 CH₂ 6-chloro-2-pyridyl 91 CH₂ 6-methoxy-2-pyridyl 92 CH₂ 6-trifluoromethyl-2-pyridyl 93 CH₂ 3-pyridyl 94 CH₂ 2-chloro-3-pyridyl 95 CH₂ 2-methoxy-3-pyridyl 96 CH₂ 4-pyridyl 97 CH₂ 2-chloro-4-pyridyl 98 CH₂ 2-methoxy-4-pyridyl 99 CH₂ 2-ethoxy-4-pyridyl 100 CH₂ 2-methylthio-4-pyridyl 101 CH₂ 2-trifluoromethyl-5-pyridyl 102 CH₂ 2-pyrimidinyl 103 CH₂ 3-pyrimidinyl 104 CH₂ 4-pyrimidinyl 105 CH₂ 2-pyrazinyl 106 CH₂ 3-pyridazinyl 107 CH₂ 4-pyridazinyl 108 CH₂ 2-(2H-1,3-oxazinyl) 109 CH₂ 2-(6H-1,3-oxazinyl) 110 CH₂ 4-(6H-1,3-oxazinyl) 111 CH₂ 6-(6H-1,3-oxazinyl) 112 CH₂ [1,3,5]-2-triazinyl 113 CH₂ [1,2,4]-3-triazinyl 114 CH₂ [1,2,4]-5-triazinyl 115 CH₂ [1,2,4]-6-triazinyl 116 CHCH₃ oxiranyl 117 CHCH₃ 3-methyl-2-oxiranyl 118 CHCH₃ 2-oxetanyl 119 CHCH₃ 3-hydroxy-3-methyl-2-oxetanyl 120 CHCH₃ 3-hydroxy-3-ethyl-2-oxetanyl 121 CHCH₃ 3-hydroxy-3-propyl-2-oxetanyl 122 CHCH₃ 3-hydroxy-3-butyl-2-oxetanyl 123 CHCH₃ 3-methoxy-3-methyl-2-oxetanyl 124 CHCH₃ 3-methoxy-3-ethyl-2-oxetanyl 125 CHCH₃ 3-methoxy-3-propyl-2-oxetanyl 126 CHCH₃ 3-methoxy-3-butyl-2-oxetanyl 127 CHCH₃ 3-trimethylsilyloxy-3-methyl-2-oxetanyl 128 CHCH₃ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 129 CHCH₃ 3-trimethylsilyloxy-3-propyl-2-oxetanyl 130 CHCH₃ 3-trimethylsilyloxy-3-butyl-2-oxetanyl 131 CHCH₃ 3-oxetanyl 132 CHCH₃ 2-furyl 133 CHCH₃ 4,5-dihydro-2-furyl 134 CHCH₃ 2,3-dihydro-2-furyl 135 CHCH₃ 3-furyl 136 CHCH₃ 4,5-dihydro-3-furyl 137 CHCH₃ 2,3-dihydro-3-furyl 138 CHCH₃ 2-thienyl 139 CHCH₃ 4,5-dihydro-2-thienyl 140 CHCH₃ 2,3-dihydro-2-thienyl 141 CHCH₃ 5-chloro-2-thienyl 142 CHCH₃ 5-methyl-2-thienyl 143 CHCH₃ 3-thienyl 144 CHCH₃ 4,5-dihydro-3-thienyl 145 CHCH₃ 2,3-dihydro-3-thienyl 146 CHCH₃ 2-pyrrolyl 147 CHCH₃ 2,5-dihydro-2-pyrrolyl 148 CHCH₃ 3-pyrrolyl 149 CHCH₃ 2,5-dihydro-3-pyrrolyl 150 CHCH₃ 3-isoxazolyl 151 CHCH₃ 4-methyl-3-isoxazolyl 152 CHCH₃ 5-methyl-3-isoxazolyl 153 CHCH₃ 4,5-dimethyl-3-isoxazolyl 154 CHCH₃ 4,5-dihydro-3-isoxazolyl 155 CHCH₃ 4-methyl-4,5-dihydro-3-isoxazolyl 156 CHCH₃ 5-methyl-4,5-dihydro-3-isoxazolyl 157 CHCH₃ 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 158 CHCH₃ 4-isoxazolyl 159 CHCH₃ 3-methyl-4-isoxazolyl 160 CHCH₃ 5-methyl-4-isoxazolyl 161 CHCH₃ 5-cyclopropyl-4-isoxazolyl 162 CHCH₃ 5-phenyl-4-isoxazolyl 163 CHCH₃ 3,5-dimethyl-4-isoxazolyl 164 CHCH₃ 4,5-dihydro-4-isoxazolyl 165 CHCH₃ 3-methyl-4,5-dihydro-4-isoxazolyl 166 CHCH₃ 5-methyl-4,5-dihydro-4-isoxazolyl 167 CHCH₃ 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 168 CHCH₃ 5-isoxazolyl 169 CHCH₃ 3-methyl-5-isoxazolyl 170 CHCH₃ 4-methyl-5-isoxazolyl 171 CHCH₃ 3,4-dimethyl-5-isoxazolyl 172 CHCH₃ 4,5-dihydro-3-isoxazolyl 173 CHCH₃ 3-methyl-4,5-dihydro-5-isoxazolyl 174 CHCH₃ 4-methyl-4,5-dihydro-5-isoxazolyl 175 CHCH₃ 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 176 CHCH₃ 3-isothiazolyl 177 CHCH₃ 4-methyl-3-isothiazolyl 178 CHCH₃ 5-methyl-3-isothiazolyl 179 CHCH₃ 4-isothiazolyl 180 CHCH₃ 3-methyl-4-isothiazolyl 181 CHCH₃ 5-methyl-4-isothiazolyl 182 CHCH₃ 5-isothiazolyl 183 CHCH₃ 3-methyl-5-isothiazolyl 184 CHCH₃ 4-methyl-5-isothiazolyl 185 CHCH₃ 2-oxazolyl 186 CHCH₃ 4-oxazolyl 187 CHCH₃ 5-oxazolyl 188 CHCH₃ 2-thiazolyl 189 CHCH₃ 4-thiazolyl 190 CHCH₃ 5-thiazolyl 191 CHCH₃ 3-pyrazolyl 192 CHCH₃ 4-pyrazolyl 193 CHCH₃ 1-methyl-3-pyrazolyl 194 CHCH₃ 1-methyl-4-pyrazolyl 195 CHCH₃ 1-methyl-5-pyrazolyl 196 CHCH₃ 2-imidazolyl 197 CHCH₃ 1-methyl-2-imidazolyl 198 CHCH₃ 5-methyl-[1,3,4]-2-oxadiazolyl 199 CHCH₃ 5-methyl-[1,2,4]-3-oxadiazolyl 200 CHCH₃ 5-methyl-[1,3,4]-2-thiadiazolyl 201 CHCH₃ 5-methyl-[1,2,4]-3-thiadiazolyl 202 CHCH₃ [1,2,4]-3-triazolyl 203 CHCH₃ [1,2,3]-4-triazolyl 204 CHCH₃ 2-pyridyl 205 CHCH₃ 6-chloro-2-pyridyl 206 CHCH₃ 6-methoxy-2-pyridyl 207 CHCH₃ 6-trifluoromethyl-2-pyridyl 208 CHCH₃ 3-pyridyl 209 CHCH₃ 2-chloro-3-pyridyl 210 CHCH₃ 2-methoxy-3-pyridyl 211 CHCH₃ 4-pyridyl 212 CHCH₃ 2-chloro-4-pyridyl 213 CHCH₃ 2-methoxy-4-pyridyl 214 CHCH₃ 2-ethoxy-4-pyridyl 215 CHCH₃ 2-methylthio-4-pyridyl 216 CHCH₃ 2-trifluoromethyl-5-pyridyl 217 CHCH₃ 2-pyrimidinyl 218 CHCH₃ 3-pyrimidinyl 219 CHCH₃ 4-pyrimidinyl 220 CHCH₃ 2-pyrazinyl 221 CHCH₃ 3-pyridazinyl 222 CHCH₃ 4-pyridazinyl 223 CHCH₃ 2-(2H-1,3-oxazinyl) 224 CHCH₃ 2-(6H-1,3-oxazinyl) 225 CHCH₃ 4-(6H-1,3-oxazinyl) 226 CHCH₃ 6-(6H-1,3-oxazinyl) 227 CHCH₃ [1,3,5]-2-triazinyl 228 CHCH₃ [1,2,4]-3-triazinyl 229 CHCH₃ [1,2,4]-5-triazinyl 230 CHCH₃ [1,2,4]-6-triazinyl 231 CHOH oxiranyl 232 CHOH 3-methyl-2-oxiranyl 233 CHOH 2-oxetanyl 234 CHOH 3-hydroxy-3-methyl-2-oxetanyl 235 CHOH 3-hydroxy-3-ethyl-2-oxetanyl 236 CHOH 3-hydroxy-3-propyl-2-oxetanyl 237 CHOH 3-hydroxy-3-butyl-2-oxetanyl 238 CHOH 3-methoxy-3-methyl-2-oxetanyl 239 CHOH 3-methoxy-3-ethyl-2-oxetanyl 240 CHOH 3-methoxy-3-propyl-2-oxetanyl 241 CHOH 3-methoxy-3-butyl-2-oxetanyl 242 CHOH 3-trimethylsilyloxy-3-methyl-2-oxetanyl 243 CHOH 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 244 CHOH 3-trimethylsilyloxy-3-propyl-2-oxetanyl 245 CHOH 3-trimethylsilyloxy-3-butyl-2-oxetanyl 246 CHOH 3-oxetanyl 247 CHOH 2-furyl 248 CHOH 4,5-dihydro-2-furyl 249 CHOH 2,3-dihydro-2-furyl 250 CHOH 3-furyl 251 CHOH 4,5-dihydro-3-furyl 252 CHOH 2,3-dihydro-3-furyl 253 CHOH 2-thienyl 254 CHOH 4,5-dihydro-2-thienyl 255 CHOH 2,3-dihydro-2-thienyl 256 CHOH 5-chloro-2-thienyl 257 CHOH 5-methyl-2-thienyl 258 CHOH 3-thienyl 259 CHOH 4,5-dihydro-3-thienyl 260 CHOH 2,3-dihydro-3-thienyl 261 CHOH 2-pyrrolyl 262 CHOH 2,5-dihydro-2-pyrrolyl 263 CHOH 3-pyrrolyl 264 CHOH 2,5-dihydro-3-pyrrolyl 265 CHOH 3-isoxazolyl 266 CHOH 4-methyl-3-isoxazolyl 267 CHOH 5-methyl-3-isoxazolyl 268 CHOH 4,5-dimethyl-3-isoxazolyl 269 CHOH 4,5-dihydro-3-isoxazolyl 270 CHOH 4-methyl-4,5-dihydro-3-isoxazolyl 271 CHOH 5-methyl-4,5-dihydro-3-isoxazolyl 272 CHOH 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 273 CHOH 4-isoxazolyl 274 CHOH 3-methyl-4-isoxazolyl 275 CHOH 5-methyl-4-isoxazolyl 276 CHOH 5-cyclopropyl-4-isoxazolyl 277 CHOH 5-phenyl-4-isoxazolyl 278 CHOH 3,5-dimethyl-4-isoxazolyl 279 CHOH 4,5-dihydro-4-isoxazolyl 280 CHOH 3-methyl-4,5-dihydro-4-isoxazolyl 281 CHOH 5-methyl-4,5-dihydro-4-isoxazolyl 282 CHOH 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 283 CHOH 5-isoxazolyl 284 CHOH 3-methyl-5-isoxazolyl 285 CHOH 4-methyl-5-isoxazolyl 286 CHOH 3,4-dimethyl-5-isoxazolyl 287 CHOH 4,5-dihydro-3-isoxazolyl 288 CHOH 3-methyl-4,5-dihydro-5-isoxazolyl 289 CHOH 4-methyl-4,5-dihydro-5-isoxazolyl 290 CHOH 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 291 CHOH 3-isothiazolyl 292 CHOH 4-methyl-3-isothiazolyl 293 CHOH 5-methyl-3-isothiazolyl 294 CHOH 4-isothiazolyl 295 CHOH 3-methyl-4-isothiazolyl 296 CHOH 5-methyl-4-isothiazolyl 297 CHOH 5-isothiazolyl 298 CHOH 3-methyl-5-isothiazolyl 299 CHOH 4-methyl-5-isothiazolyl 300 CHOH 2-oxazolyl 301 CHOH 4-oxazolyl 302 CHOH 5-oxazolyl 303 CHOH 2-thiazolyl 304 CHOH 4-thiazolyl 305 CHOH 5-thiazolyl 306 CHOH 3-pyrazolyl 307 CHOH 4-pyrazolyl 308 CHOH 1-methyl-3-pyrazolyl 309 CHOH 1-methyl-4-pyrazolyl 310 CHOH 1-methyl-5-pyrazolyl 311 CHOH 2-imidazolyl 312 CHOH 1-methyl-2-imidazolyl 313 CHOH 5-methyl-[1,3,4]-2-oxadiazolyl 314 CHOH 5-methyl-[1,2,4]-3-oxadiazolyl 315 CHOH 5-methyl-[1,3,4]-2-thiadiazolyl 316 CHOH 5-methyl-[1,2,4]-3-thiadiazolyl 317 CHOH [1,2,4]-3-triazolyl 318 CHOH [1,2,3]-4-triazolyl 319 CHOH 2-pyridyl 320 CHOH 6-chloro-2-pyridyl 321 CHOH 6-methoxy-2-pyridyl 322 CHOH 6-trifluoromethyl-2-pyridyl 323 CHOH 3-pyridyl 324 CHOH 2-chloro-3-pyridyl 325 CHOH 2-methoxy-3-pyridyl 326 CHOH 4-pyridyl 327 CHOH 2-chloro-4-pyridyl 328 CHOH 2-methoxy-4-pyridyl 329 CHOH 2-ethoxy-4-pyridyl 330 CHOH 2-methylthio-4-pyridyl 331 CHOH 2-trifluoromethyl-5-pyridyl 332 CHOH 2-pyrimidinyl 333 CHOH 3-pyrimidinyl 334 CHOH 4-pyrimidinyl 335 CHOH 2-pyrazinyl 336 CHOH 3-pyridazinyl 337 CHOH 4-pyridazinyl 338 CHOH 2-(2H-1,3-oxazinyl) 339 CHOH 2-(6H-1,3-oxazinyl) 340 CHOH 4-(6H-1,3-oxazinyl) 341 CHOH 6-(6H-1,3-oxazinyl) 342 CHOH [1,3,5]-2-triazinyl 343 CHOH [1,2,4]-3-triazinyl 344 CHOH [1,2,4]-5-triazinyl 345 CHOH [1,2,4]-6-triazinyl 346 CHOCH₃ oxiranyl 347 CHOCH₃ 3-methyl-2-oxiranyl 348 CHOCH₃ 2-oxetanyl 349 CHOCH₃ 3-hydroxy-3-methyl-2-oxetanyl 350 CHOCH₃ 3-hydroxy-3-ethyl-2-oxetanyl 351 CHOCH₃ 3-hydroxy-3-propyl-2-oxetanyl 352 CHOCH₃ 3-hydroxy-3-butyl-2-oxetanyl 353 CHOCH₃ 3-methoxy-3-methyl-2-oxetanyl 354 CHOCH₃ 3-methoxy-3-ethyl-2-oxetanyl 355 CHOCH₃ 3-methoxy-3-propyl-2-oxetanyl 356 CHOCH₃ 3-methoxy-3-butyl-2-oxetanyl 357 CHOCH₃ 3-trimethylsilyloxy-3-methyl-2-oxetanyl 358 CHOCH₃ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 359 CHOCH₃ 3-trimethylsilyloxy-3-propyl-2-oxetanyl 360 CHOCH₃ 3-trimethylsilyloxy-3-butyl-2-oxetanyl 361 CHOCH₃ 3-oxetanyl 362 CHOCH₃ 2-furyl 363 CHOCH₃ 4,5-dihydro-2-furyl 364 CHOCH₃ 2,3-dihydro-2-furyl 365 CHOCH₃ 3-furyl 366 CHOCH₃ 4,5-dihydro-3-furyl 367 CHOCH₃ 2,3-dihydro-3-furyl 368 CHOCH₃ 2-thienyl 369 CHOCH₃ 4,5-dihydro-2-thienyl 370 CHOCH₃ 2,3-dihydro-2-thienyl 371 CHOCH₃ 5-chloro-2-thienyl 372 CHOCH₃ 5-methyl-2-thienyl 373 CHOCH₃ 3-thienyl 374 CHOCH₃ 4,5-dihydro-3-thienyl 375 CHOCH₃ 2,3-dihydro-3-thienyl 376 CHOCH₃ 2-pyrrolyl 377 CHOCH₃ 2,5-dihydro-2-pyrrolyl 378 CHOCH₃ 3-pyrrolyl 379 CHOCH₃ 2,5-dihydro-3-pyrrolyl 380 CHOCH₃ 3-isoxazolyl 381 CHOCH₃ 4-methyl-3-isoxazolyl 382 CHOCH₃ 5-methyl-3-isoxazolyl 383 CHOCH₃ 4,5-dimethyl-3-isoxazolyl 384 CHOCH₃ 4,5-dihydro-3-isoxazolyl 385 CHOCH₃ 4-methyl-4,5-dihydro-3-isoxazolyl 386 CHOCH₃ 5-methyl-4,5-dihydro-3-isoxazolyl 387 CHOCH₃ 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 388 CHOCH₃ 4-isoxazolyl 389 CHOCH₃ 3-methyl-4-isoxazolyl 390 CHOCH₃ 5-methyl-4-isoxazolyl 391 CHOCH₃ 5-cyclopropyl-4-isoxazolyl 392 CHOCH₃ 5-phenyl-4-isoxazolyl 393 CHOCH₃ 3,5-dimethyl-4-isoxazolyl 394 CHOCH₃ 4,5-dihydro-4-isoxazolyl 395 CHOCH₃ 3-methyl-4,5-dihydro-4-isoxazolyl 396 CHOCH₃ 5-methyl-4,5-dihydro-4-isoxazolyl 397 CHOCH₃ 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 398 CHOCH₃ 5-isoxazolyl 399 CHOCH₃ 3-methyl-5-isoxazolyl 400 CHOCH₃ 4-methyl-5-isoxazolyl 401 CHOCH₃ 3,4-dimethyl-5-isoxazolyl 402 CHOCH₃ 4,5-dihydro-5-isoxazolyl 403 CHOCH₃ 3-methyl-4,5-dihydro-5-isoxazolyl 404 CHOCH₃ 4-methyl-4,5-dihydro-5-isoxazolyl 405 CHOCH₃ 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 406 CHOCH₃ 3-isothiazolyl 407 CHOCH₃ 4-methyl-3-isothiazolyl 408 CHOCH₃ 5-methyl-3-isothiazolyl 409 CHOCH₃ 4-isothiazolyl 410 CHOCH₃ 3-methyl-4-isothiazolyl 411 CHOCH₃ 5-methyl-4-isothiazolyl 412 CHOCH₃ 5-isothiazolyl 413 CHOCH₃ 3-methyl-5-isothiazolyl 414 CHOCH₃ 4-methyl-5-isothiazolyl 415 CHOCH₃ 2-oxazolyl 416 CHOCH₃ 4-oxazolyl 417 CHOCH₃ 5-oxazolyl 418 CHOCH₃ 2-thiazolyl 419 CHOCH₃ 4-thiazolyl 420 CHOCH₃ 5-thiazolyl 421 CHOCH₃ 3-pyrazolyl 422 CHOCH₃ 4-pyrazolyl 423 CHOCH₃ 1-methyl-3-pyrazolyl 424 CHOCH₃ 1-methyl-4-pyrazolyl 425 CHOCH₃ 1-methyl-5-pyrazolyl 426 CHOCH₃ 2-imidazolyl 427 CHOCH₃ 1-methyl-2-imidazolyl 428 CHOCH₃ 5-methyl-[1,3,4]-2-oxadiazolyl 429 CHOCH₃ 5-methyl-[1,2,4]-3-oxadiazolyl 430 CHOCH₃ 5-methyl-[1,3,4]-2-thiadiazolyl 431 CHOCH₃ 5-methyl-[1,2,4]-3-thiadiazolyl 432 CHOCH₃ [1,2,4]-3-triazolyl 433 CHOCH₃ [1,2,3]-4-triazolyl 434 CHOCH₃ 2-pyridyl 435 CHOCH₃ 6-chloro-2-pyridyl 436 CHOCH₃ 6-methoxy-2-pyridyl 437 CHOCH₃ 6-trifluoromethyl-2-pyridyl 438 CHOCH₃ 3-pyridyl 439 CHOCH₃ 2-chloro-3-pyridyl 440 CHOCH₃ 2-methoxy-3-pyridyl 441 CHOCH₃ 4-pyridyl 442 CHOCH₃ 2-chloro-4-pyridyl 443 CHOCH₃ 2-methoxy-4-pyridyl 444 CHOCH₃ 2-ethoxy-4-pyridyl 445 CHOCH₃ 2-methylthio-4-pyridyl 446 CHOCH₃ 2-trifluoromethyl-5-pyridyl 447 CHOCH₃ 2-pyrimidinyl 448 CHOCH₃ 3-pyrimidinyl 449 CHOCH₃ 4-pyrimidinyl 450 CHOCH₃ 2-pyrazinyl 451 CHOCH₃ 3-pyridazinyl 452 CHOCH₃ 4-pyridazinyl 453 CHOCH₃ 2-(2H-1,3-oxazinyl) 454 CHOCH₃ 2-(6H-1,3-oxazinyl) 455 CHOCH₃ 4-(6H-1,3-oxazinyl) 456 CHOCH₃ 6-(6H-1,3-oxazinyl) 457 CHOCH₃ [1,3,5]-2-triazinyl 458 CHOCH₃ [1,2,4]-3-triazinyl 459 CHOCH₃ [1,2,4]-5-triazinyl 460 CHOCH₃ [1,2,4]-6-triazinyl 461 CHOCOCH₃ oxiranyl 462 CHOCOCH₃ 3-methyl-2-oxiranyl 463 CHOCOCH₃ 2-oxetanyl 464 CHOCOCH₃ 3-hydroxy-3-methyl-2-oxetanyl 465 CHOCOCH₃ 3-hydroxy-3-ethyl-2-oxetanyl 466 CHOCOCH₃ 3-hydroxy-3-propyl-2-oxetanyl 467 CHOCOCH₃ 3-hydroxy-3-butyl-2-oxetanyl 468 CHOCOCH₃ 3-methoxy-3-methyl-2-oxetanyl 469 CHOCOCH₃ 3-methoxy-3-ethyl-2-oxetanyl 470 CHOCOCH₃ 3-methoxy-3-propyl-2-oxetanyl 471 CHOCOCH₃ 3-methoxy-3-butyl-2-oxetanyl 472 CHOCOCH₃ 3-trimethylsilyloxy-3-methyl-2-oxetanyl 473 CHOCOCH₃ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 474 CHOCOCH₃ 3-trimethylsilyloxy-3-propyl-2-oxetanyl 475 CHOCOCH₃ 3-trimethylsilyloxy-3-butyl-2-oxetanyl 476 CHOCOCH₃ 3-oxetanyl 477 CHOCOCH₃ 2-furyl 478 CHOCOCH₃ 4,5-dihydro-2-furyl 479 CHOCOCH₃ 2,3-dihydro-2-furyl 480 CHOCOCH₃ 3-furyl 481 CHOCOCH₃ 4,5-dihydro-3-furyl 482 CHOCOCH₃ 2,3-dihydro-3-furyl 483 CHOCOCH₃ 2-thienyl 484 CHOCOCH₃ 4,5-dihydro-2-thienyl 485 CHOCOCH₃ 2,3-dihydro-2-thienyl 486 CHOCOCH₃ 5-chloro-2-thienyl 487 CHOCOCH₃ 5-methyl-2-thienyl 488 CHOCOCH₃ 3-thienyl 489 CHOCOCH₃ 4,5-dihydro-3-thienyl 490 CHOCOCH₃ 2,3-dihydro-3-thienyl 491 CHOCOCH₃ 2-pyrrolyl 492 CHOCOCH₃ 2,5-dihydro-2-pyrrolyl 493 CHOCOCH₃ 3- pyrrolyl 494 CHOCOCH₃ 2,5-dihydro-3-pyrrolyl 495 CHOCOCH₃ 3-isoxazolyl 496 CHOCOCH₃ 4-methyl-3-isoxazolyl 497 CHOCOCH₃ 5-methyl-3-isoxazolyl 498 CHOCOCH₃ 4,5-dimethyl-3-isoxazolyl 499 CHOCOCH₃ 4,5-dihydro-3-isoxazolyl 500 CHOCOCH₃ 4-methyl-4,5-dihydro-3-isoxazolyl 501 CHOCOCH₃ 5-methyl-4,5-dihydro-3-isoxazolyl 502 CHOCOCH₃ 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 503 CHOCOCH₃ 4-isoxazolyl 504 CHOCOCH₃ 3-methyl-4-isoxazolyl 505 CHOCOCH₃ 5-methyl-4-isoxazolyl 506 CHOCOCH₃ 5-cyclopropyl-4-isoxazolyl 507 CHOCOCH₃ 5-phenyl-4-isoxazolyl 508 CHOCOCH₃ 3,5-dimethyl-4-isoxazolyl 509 CHOCOCH₃ 4,5-dihydro-4-isoxazolyl 510 CHOCOCH₃ 3-methyl-4,5-dihydro-4-isoxazolyl 511 CHOCOCH₃ 5-methyl-4,5-dihydro-4-isoxazolyl 512 CHOCOCH₃ 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 513 CHOCOCH₃ 5-isoxazolyl 514 CHOCOCH₃ 3-methyl-5-isoxazolyl 515 CHOCOCH₃ 4-methyl-5-isoxazolyl 516 CHOCOCH₃ 3,4-dimethyl-5-isoxazolyl 517 CHOCOCH₃ 4,5-dihydro-5-isoxazolyl 518 CHOCOCH₃ 3-methyl-4,5-dihydro-5-isoxazolyl 519 CHOCOCH₃ 4-methyl-4,5-dihydro-5-isoxazolyl 520 CHOCOCH₃ 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 521 CHOCOCH₃ 3-isothiazolyl 522 CHOCOCH₃ 4-methyl-3-isothiazolyl 523 CHOCOCH₃ 5-methyl-3-isothiazolyl 524 CHOCOCH₃ 4-isothiazolyl 525 CHOCOCH₃ 3-methyl-4-isothiazolyl 526 CHOCOCH₃ 5-methyl-4-isothiazolyl 527 CHOCOCH₃ 5-isothiazolyl 528 CHOCOCH₃ 3-methyl-5-isothiazolyl 529 CHOCOCH₃ 4-methyl-5-isothiazolyl 530 CHOCOCH₃ 2-oxazolyl 531 CHOCOCH₃ 4-oxazolyl 532 CHOCOCH₃ 5-oxazolyl 533 CHOCOCH₃ 2-thiazolyl 534 CHOCOCH₃ 4-thiazolyl 535 CHOCOCH₃ 5-thiazolyl 536 CHOCOCH₃ 3-pyrazolyl 537 CHOCOCH₃ 4-pyrazolyl 538 CHOCOCH₃ 1-methyl-3-pyrazolyl 539 CHOCOCH₃ 1-methyl-4-pyrazolyl 540 CHOCOCH₃ 1-methyl-5-pyrazolyl 541 CHOCOCH₃ 2-imidazolyl 542 CHOCOCH₃ 1-methyl-2-imidazolyl 543 CHOCOCH₃ 5-methyl-[1,3,4]-2-oxadiazolyl 544 CHOCOCH₃ 5-methyl-[1,2,4]-3-oxadiazolyl 545 CHOCOCH₃ 5-methyl-[1,3,4]-2-oxadiazolyl 546 CHOCOCH₃ 5-methyl-[1,2,4]-3-thiadiazolyl 547 CHOCOCH₃ [1,2,4]-3-triazolyl 548 CHOCOCH₃ [1,2,3]-4-triazolyl 549 CHOCOCH₃ 2-pyridyl 550 CHOCOCH₃ 6-chloro-2-pyridyl 551 CHOCOCH₃ 6-methoxy-2-pyridyl 552 CHOCOCH₃ 6-trifluoromethyl-2-pyridyl 553 CHOCOCH₃ 3-pyridyl 554 CHOCOCH₃ 2-chloro-3-pyridyl 555 CHOCOCH₃ 2-methoxy-3-pyridyl 556 CHOCOCH₃ 4-pyridyl 557 CHOCOCH₃ 2-chloro-4-pyridyl 558 CHOCOCH₃ 2-methoxy-4-pyridyl 559 CHOCOCH₃ 2-ethoxy-4-pyridyl 560 CHOCOCH₃ 2-methylthio-4-pyridyl 561 CHOCOCH₃ 2-trifluoromethyl-5-pyridyl 562 CHOCOCH₃ 2-pyrimidinyl 563 CHOCOCH₃ 3-pyrimidinyl 564 CHOCOCH₃ 4-pyrimidinyl 565 CHOCOCH₃ 2-pyrazinyl 566 CHOCOCH₃ 3-pyridazinyl 567 CHOCOCH₃ 4-pyridazinyl 568 CHOCOCH₃ 2-(2H-1,3-oxazinyl) 569 CHOCOCH₃ 2-(6H-1,3-oxazinyl) 570 CHOCOCH₃ 4-(6H-1,3-oxazinyl) 571 CHOCOCH₃ 6-(6H-1,3-oxazinyl) 572 CHOCOCH₃ [1,3,5]-2-triazinyl 573 CHOCOCH₃ [1,2,4]-3-triazinyl 574 CHOCOCH₃ [1,2,4]-5-triazinyl 575 CHOCOCH₃ [1,2,4]-6-triazinyl 576 CHOSO₂CH₃ oxiranyl 577 CHOSO₂CH₃ 3-methyl-2-oxiranyl 578 CHOSO₂CH₃ 2-oxetanyl 579 CHOSO₂CH₃ 3-hydroxy-3-methyl-2-oxetanyl 580 CHOSO₂CH₃ 3-hydroxy-3-ethyl-2-oxetanyl 581 CHOSO₂CH₃ 3-hydroxy-3-propyl-2-oxetanyl 582 CHOSO₂CH₃ 3-hydroxy-3-butyl-2-oxetanyl 583 CHOSO₂CH₃ 3-methoxy-3-methyl-2-oxetanyl 584 CHOSO₂CH₃ 3-methoxy-3-ethyl-2-oxetanyl 585 CHOSO₂CH₃ 3-methoxy-3-propyl-2-oxetanyl 586 CHOSO₂CH₃ 3-methoxy-3-butyl-2-oxetanyl 587 CHOSO₂CH₃ 3-trimethylsilyloxy-3-methyl-2-oxetanyl 588 CHOSO₂CH₃ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 589 CHOSO₂CH₃ 3-trimethylsilyloxy-3-propyl-2-oxetanyl 590 CHOSO₂CH₃ 3-trimethylsilyloxy-3-butyl-2-oxetanyl 591 CHOSO₂CH₃ 3-oxetanyl 592 CHOSO₂CH₃ 2-furyl 593 CHOSO₂CH₃ 4,5-dihydro-2-furyl 594 CHOSO₂CH₃ 2,3-dihydro-2-furyl 595 CHOSO₂CH₃ 3-furyl 596 CHOSO₂CH₃ 4,5-dihydro-3-furyl 597 CHOSO₂CH₃ 2,3-dihydro-3-furyl 598 CHOSO₂CH₃ 2-thienyl 599 CHOSO₂CH₃ 4,5-dihydro-2-thienyl 600 CHOSO₂CH₃ 2,3-dihydro-2-thienyl 601 CHOSO₂CH₃ 5-chloro-2-thienyl 602 CHOSO₂CH₃ 5-methyl-2-thienyl 603 CHOSO₂CH₃ 3-thienyl 604 CHOSO₂CH₃ 4,5-dihydro-3-thienyl 605 CHOSO₂CH₃ 2,3-dihydro-3-thienyl 606 CHOSO₂CH₃ 2-pyrrolyl 607 CHOSO₂CH₃ 2,5-dihydro-2-pyrrolyl 608 CHOSO₂CH₃ 3-pyrrolyl 609 CHOSO₂CH₃ 2,5-dihydro-3-pyrrolyl 610 CHOSO₂CH₃ 3-isoxazolyl 611 CHOSO₂CH₃ 4-methyl-3-isoxazolyl 612 CHOSO₂CH₃ 5-methyl-3-isoxazolyl 613 CHOSO₂CH₃ 4,5-dimethyl-3-isoxazolyl 614 CHOSO₂CH₃ 4,5-dihydro-3-isoxazolyl 615 CHOSO₂CH₃ 4-methyl-4,5-dihydro-3-isoxazolyl 616 CHOSO₂CH₃ 5-methyl-4,5-dihydro-3-isoxazolyl 617 CHOSO₂CH₃ 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 618 CHOSO₂CH₃ 4-isoxazolyl 619 CHOSO₂CH₃ 3-methyl-4-isoxazolyl 620 CHOSO₂CH₃ 5-methyl-4-isoxazolyl 621 CHOSO₂CH₃ 5-cyclopropyl-4-isoxazolyl 622 CHOSO₂CH₃ 5-phenyl-4-isoxazolyl 623 CHOSO₂CH₃ 3,5-dimethyl-4-isoxazolyl 624 CHOSO₂CH₃ 4,5-dihydro-4-isoxazolyl 625 CHOSO₂CH₃ 3-methyl-4,5-dihydro-4-isoxazolyl 626 CHOSO₂CH₃ 5-methyl-4,5-dihydro-4-isoxazolyl 627 CHOSO₂CH₃ 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 628 CHOSO₂CH₃ 5-isoxazolyl 629 CHOSO₂CH₃ 3-methyl-5-isoxazolyl 630 CHOSO₂CH₃ 4-methyl-5-isoxazolyl 631 CHOSO₂CH₃ 3,4-dimethyl-5-isoxazolyl 632 CHOSO₂CH₃ 4,5-dihydro-5-isoxazolyl 633 CHOSO₂CH₃ 3-methyl-4,5-dihydro-5-isoxazolyl 634 CHOSO₂CH₃ 4-methyl-4,5-dihydro-5-isoxazolyl 635 CHOSO₂CH₃ 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 636 CHOSO₂CH₃ 3-isothiazolyl 637 CHOSO₂CH₃ 4-methyl-3-isothiazolyl 638 CHOSO₂CH₃ 5-methyl-3-isothiazolyl 639 CHOSO₂CH₃ 4-isothiazolyl 640 CHOSO₂CH₃ 3-methyl-4-isothiazolyl 641 CHOSO₂CH₃ 5-methyl-4-isothiazolyl 642 CHOSO₂CH₃ 5-isothiazolyl 643 CHOSO₂CH₃ 3-methyl-5-isothiazolyl 644 CHOSO₂CH₃ 4-methyl-5-isothiazolyl 645 CHOSO₂CH₃ 2-oxazolyl 646 CHOSO₂CH₃ 4-oxazolyl 647 CHOSO₂CH₃ 5-oxazolyl 648 CHOSO₂CH₃ 2-thiazolyl 649 CHOSO₂CH₃ 4-thiazolyl 650 CHOSO₂CH₃ 5-thiazolyl 651 CHOSO₂CH₃ 3-pyrazolyl 652 CHOSO₂CH₃ 4-pyrazolyl 653 CHOSO₂CH₃ 1-methyl-3-pyrazolyl 654 CHOSO₂CH₃ 1-methyl-4-pyrazolyl 655 CHOSO₂CH₃ 1-methyl-5-pyrazolyl 656 CHOSO₂CH₃ 2-imidazolyl 657 CHOSO₂CH₃ 1-methyl-2-imidazolyl 658 CHOSO₂CH₃ 5-methyl-[1,3,4]-2-oxadiazolyl 659 CHOSO₂CH₃ 5-methyl-[1,2,4]-3-oxadiazolyl 660 CHOSO₂CH₃ 5-methyl-[1,3,4]-2-thiadiazolyl 661 CHOSO₂CH₃ 5-methyl-[1,2,4]-3-thiadiazolyl 662 CHOSO₂CH₃ [1,2,4]-3-triazolyl 663 CHOSO₂CH₃ [1,2,3]-4-triazolyl 664 CHOSO₂CH₃ 2-pyridyl 665 CHOSO₂CH₃ 6-chloro-2-pyridyl 666 CHOSO₂CH₃ 6-methoxy-2-pyridyl 667 CHOSO₂CH₃ 6-trifluoromethyl-2-pyridyl 668 CHOSO₂CH₃ 3-pyridyl 669 CHOSO₂CH₃ 2-chloro-3-pyridyl 670 CHOSO₂CH₃ 2-methoxy-3-pyridyl 671 CHOSO₂CH₃ 4-pyridyl 672 CHOSO₂CH₃ 2-chlor-4-pyridyl 673 CHOSO₂CH₃ 2-methoxy-4-pyridyl 674 CHOSO₂CH₃ 2-ethoxy-4-pyridyl 675 CHOSO₂CH₃ 2-methylthio-4-pyridyl 676 CHOSO₂CH₃ 2-trifluoromethyl-5-pyridyl 677 CHOSO₂CH₃ 2-pyrimidinyl 678 CHOSO₂CH₃ 3-pyrimidinyl 679 CHOSO₂CH₃ 4-pyrimidinyl 680 CHOSO₂CH₃ 2-pyrazinyl 681 CHOSO₂CH₃ 3-pyridazinyl 682 CHOSO₂CH₃ 4-pyridazinyl 683 CHOSO₂CH₃ 2-(2H-1,3-oxazinyl) 684 CHOSO₂CH₃ 2-(6H-1,3-oxazinyl) 685 CHOSO₂CH₃ 4-(6H-1,3-oxazinyl) 686 CHOSO₂CH₃ 6-(6H-1,3-oxazinyl) 687 CHOSO₂CH₃ [1,3,5]-2-triazinyl 688 CHOSO₂CH₃ [1,2,4]-3-triazinyl 689 CHOSO₂CH₃ [1,2,4]-5-triazinyl 690 CHOSO₂CH₃ [1,2,4]-6-triazinyl 691 CH₂CH₂ oxiranyl 692 CH₂CH₂ 3-methyl-2-oxiranyl 693 CH₂CH₂ 2-oxetanyl 694 CH₂CH₂ 3-hydroxy-3-methyl-2-oxetanyl 695 CH₂CH₂ 3-hydroxy-3-ethyl-2-oxetanyl 696 CH₂CH₂ 3-hydroxy-3-propyl-2-oxetanyl 697 CH₂CH₂ 3-hydroxy-3-butyl-2-oxetanyl 698 CH₂CH₂ 3-methoxy-3-methyl-2-oxetanyl 699 CH₂CH₂ 3-methoxy-3-ethyl-2-oxetanyl 700 CH₂CH₂ 3-methoxy-3-propyl-2-oxetanyl 701 CH₂CH₂ 3-methoxy-3-butyl-2-oxetanyl 702 CH₂CH₂ 3-trimethylsilyloxy-3-methyl-2-oxetanyl 703 CH₂CH₂ 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 704 CH₂CH₂ 3-trimethylsilyloxy-3-propyl-2-oxetanyl 705 CH₂CH₂ 3-trimethylsilyloxy-3-butyl-2-oxetanyl 706 CH₂CH₂ 3-oxetanyl 707 CH₂CH₂ 2-furyl 708 CH₂CH₂ 4,5-dihydro-2-furyl 709 CH₂CH₂ 2,3-dihydro-2-furyl 710 CH₂CH₂ 3-furyl 711 CH₂CH₂ 4,5-dihydro-3-furyl 712 CH₂CH₂ 2,3-dihydro-3-furyl 713 CH₂CH₂ 2-thienyl 714 CH₂CH₂ 4,5-dihydro-2-thienyl 715 CH₂CH₂ 2,3-dihydro-2-thienyl 716 CH₂CH₂ 5-chloro-2-thienyl 717 CH₂CH₂ 5-methyl-2-thienyl 718 CH₂CH₂ 3-thienyl 719 CH₂CH₂ 4,5-dihydro-3-thienyl 720 CH₂CH₂ 2,3-dihydro-3-thienyl 721 CH₂CH₂ 2-pyrrolyl 722 CH₂CH₂ 2,5-dihydro-2-pyrrolyl 723 CH₂CH₂ 3-pyrrolyl 724 CH₂CH₂ 2,5-dihydro-3-pyrrolyl 725 CH₂CH₂ 3-isoxazolyl 726 CH₂CH₂ 4-methyl-3-isoxazolyl 727 CH₂CH₂ 5-methyl-3-isoxazolyl 728 CH₂CH₂ 4,5-dimethyl-3-isoxazolyl 729 CH₂CH₂ 4,5-dihydro-3-isoxazolyl 730 CH₂CH₂ 4-methyl-4,5-dihydro-3-isoxazolyl 731 CH₂CH₂ 5-methyl-4,5-dihydro-3-isoxazolyl 732 CH₂CH₂ 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 733 CH₂CH₂ 4-isoxazolyl 734 CH₂CH₂ 3-methyl-4-isoxazolyl 735 CH₂CH₂ 5-methyl-4-isoxazolyl 736 CH₂CH₂ 5-cyclopropyl-4-isoxazolyl 737 CH₂CH₂ 5-phenyl-4-isoxazolyl 738 CH₂CH₂ 3,5-dimethyl-4-isoxazolyl 739 CH₂CH₂ 4,5-dihydro-4-isoxazolyl 740 CH₂CH₂ 3-methyl-4,5-dihydro-4-isoxazolyl 741 CH₂CH₂ 5-methyl-4,5-dihydro-4-isoxazolyl 742 CH₂CH₂ 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 743 CH₂CH₂ 5-isoxazolyl 744 CH₂CH₂ 3-methyl-5-isoxazolyl 745 CH₂CH₂ 4-methyl-5-isoxazolyl 746 CH₂CH₂ 3,4-dimethyl-5-isoxazolyl 747 CH₂CH₂ 4,5-dihydro-5-isoxazolyl 748 CH₂CH₂ 3-methyl-4,5-dihydro-5-isoxazolyl 749 CH₂CH₂ 4-methyl-4,5-dihydro-5-isoxazolyl 750 CH₂CH₂ 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 751 CH₂CH₂ 3-isothiazolyl 752 CH₂CH₂ 4-methyl-3-isothiazolyl 753 CH₂CH₂ 5-methyl-3-isothiazolyl 754 CH₂CH₂ 4-isothiazolyl 755 CH₂CH₂ 3-methyl-4-isothiazolyl 756 CH₂CH₂ 5-methyl-4-isothiazolyl 757 CH₂CH₂ 5-isothiazolyl 758 CH₂CH₂ 3-methyl-5-isothiazolyl 759 CH₂CH₂ 4-methyl-5-isothiazolyl 760 CH₂CH₂ 2-oxazolyl 761 CH₂CH₂ 4-oxazolyl 762 CH₂CH₂ 5-oxazolyl 763 CH₂CH₂ 2-thiazolyl 764 CH₂CH₂ 4-thiazolyl 765 CH₂CH₂ 5-thiazolyl 766 CH₂CH₂ 3-pyrazolyl 767 CH₂CH₂ 4-pyrazolyl 768 CH₂CH₂ 1-methyl-3-pyrazolyl 769 CH₂CH₂ 1-methyl-4-pyrazolyl 770 CH₂CH₂ 1-methyl-5-pyrazolyl 771 CH₂CH₂ 2-imidazolyl 772 CH₂CH₂ 1-methyl-2-imidazolyl 773 CH₂CH₂ 5-methyl-[1,3,4]-2-oxadiazolyl 774 CH₂CH₂ 5-methyl-[1,2,4]-3-oxadiazolyl 775 CH₂CH₂ 5-methyl-[1,3,4]-2-thiadiazolyl 776 CH₂CH₂ 5-methyl-[1,2,4]-3-thiadiazolyl 777 CH₂CH₂ [1,2,4]-3-triazolyl 778 CH₂CH₂ [1,2,3]-3-triazolyl 779 CH₂CH₂ 2-pyridyl 780 CH₂CH₂ 6-chloro-2-pyridyl 781 CH₂CH₂ 6-methoxy-2-pyridyl 782 CH₂CH₂ 6-trifluoromethyl-2-pyridyl 783 CH₂CH₂ 3-pyridyl 784 CH₂CH₂ 2-chloro-3-pyridyl 785 CH₂CH₂ 2-methoxy-3-pyridyl 786 CH₂CH₂ 4-pyridyl 787 CH₂CH₂ 2-chloro-4-pyridyl 788 CH₂CH₂ 2-methoxy-4-pyridyl 789 CH₂CH₂ 2-ethoxy-4-pyridyl 790 CH₂CH₂ 2-methylthio-4-pyridyl 791 CH₂CH₂ 2-trifluoromethyl-5-pyridyl 792 CH₂CH₂ 2-pyrimidinyl 793 CH₂CH₂ 3-pyrimidinyl 794 CH₂CH₂ 4-pyrimidinyl 795 CH₂CH₂ 2-pyrazinyl 796 CH₂CH₂ 3-pyridazinyl 797 CH₂CH₂ 4-pyridazinyl 798 CH₂CH₂ 2-(2H-1,3-oxazinyl) 799 CH₂CH₂ 2-(6H-1,3-oxazinyl) 800 CH₂CH₂ 4-(6H-1,3-oxazinyl) 801 CH₂CH₂ 6-(6H-1,3-oxazinyl) 802 CH₂CH₂ [1,3,5]-2-triazinyl 803 CH₂CH₂ [1,2,4]-3-triazinyl 804 CH₂CH₂ [1,2,4]-5-triazinyl 805 CH₂CH₂ [1,2,4]-6-triazinyl 806 —C≡C— oxiranyl 807 —C≡C— 3-methyl-2-oxiranyl 808 —C≡C— 2-oxetanyl 809 —C≡C— 3-hydroxy-3-methyl-2-oxetanyl 810 —C≡C— 3-hydroxy-3-ethyl-2-oxetanyl 811 —C≡C— 3-hydroxy-3-propyl-2-oxetanyl 812 —C≡C— 3-hydroxy-3-butyl-2-oxetanyl 813 —C≡C— 3-methoxy-3-methyl-2-oxetanyl 814 —C≡C— 3-methoxy-3-ethyl-2-oxetanyl 815 —C≡C— 3-methoxy-3-propyl-2-oxetanyl 816 —C≡C— 3-methoxy-3-butyl-2-oxetanyl 817 —C≡C— 3-trimethylsilyloxy-3-methyl-2-oxetanyl 818 —C≡C— 3-trimethylsilyloxy-3-ethyl-2-oxetanyl 819 —C≡C— 3-trimethylsilyloxy-3-propyl-2-oxetanyl 820 —C≡C— 3-trimethylsilyloxy-3-butyl-2-oxetanyl 821 —C≡C— 3-oxetanyl 822 —C≡C— 2-furyl 823 —C≡C— 4,5-dihydro-2-furyl 824 —C≡C— 2,3-dihydro-2-furyl 825 —C≡C— 3-furyl 826 —C≡C— 4,5-dihydro-3-furyl 827 —C≡C— 2,3-dihydro-3-furyl 828 —C≡C— 2-thienyl 829 —C≡C— 4,5-dihydro-2-thienyl 830 —C≡C— 2,3-dihydro-2-thienyl 831 —C≡C— 5-chlor-2-thienyl 832 —C≡C— 5-methyl-2-thienyl 833 —C≡C— 3-thienyl 834 —C≡C— 4,5-dihydro-3-thienyl 835 —C≡C— 2,3-dihydro-3-thienyl 836 —C≡C— 2-pyrrolyl 837 —C≡C— 2,5-dihydro-2-pyrrolyl 838 —C≡C— 3-pyrrolyl 839 —C≡C— 2,5-dihydro-3-pyrrolyl 840 —C≡C— 3-isoxazolyl 841 —C≡C— 4-methyl-3-isoxazolyl 842 —C≡C— 5-methyl-3-isoxazolyl 843 —C≡C— 4,5-dimethyl-3-isoxazolyl 844 —C≡C— 4,5-dihydro-3-isoxazolyl 845 —C≡C— 4-methyl-4,5-dihydro-3-isoxazolyl 846 —C≡C— 5-methyl-4,5-dihydro-3-isoxazolyl 847 —C≡C— 4,5-dimethyl-4,5-dihydro-3-isoxazolyl 848 —C≡C— 4-isoxazolyl 849 —C≡C— 3-methyl-4-isoxazolyl 850 —C≡C— 5-methyl-4-isoxazolyl 851 —C≡C— 5-cyclopropyl-4-isoxazolyl 852 —C≡C— 5-phenyl-4-isoxazolyl 853 —C≡C— 3,5-dimethyl-4-isoxazolyl 854 —C≡C— 4,5-dihydro-4-isoxazolyl 855 —C≡C— 3-methyl-4,5-dihydro-4-isoxazolyl 856 —C≡C— 5-methyl-4,5-dihydro-4-isoxazolyl 857 —C≡C— 3,5-dimethyl-4,5-dihydro-4-isoxazolyl 858 —C≡C— 5-isoxazolyl 859 —C≡C— 3-methyl-5-isoxazolyl 860 —C≡C— 4-methyl-5-isoxazolyl 861 —C≡C— 3,4-dimethyl-5-isoxazolyl 862 —C≡C— 4,5-dihydro-5-isoxazolyl 863 —C≡C— 3-methyl-4,5-dihydro-5-isoxazolyl 864 —C≡C— 4-methyl-4,5-dihydro-5-isoxazolyl 865 —C≡C— 3,4-dimethyl-4,5-dihydro-5-isoxazolyl 866 —C≡C— 3-isothiazolyl 867 —C≡C— 4-methyl-3-isothiazolyl 868 —C≡C— 5-methyl-3-isothiazolyl 869 —C≡C— 4-isothiazolyl 870 —C≡C— 3-methyl-4-isothiazolyl 871 —C≡C— 5-methyl-4-isothiazolyl 872 —C≡C— 5-isothiazolyl 873 —C≡C— 3-methyl-5-isothiazolyl 874 —C≡C— 4-methyl-5-isothiazolyl 875 —C≡C— 2-oxazolyl 876 —C≡C— 4-oxazolyl 877 —C≡C— 5-oxazolyl 878 —C≡C— 2-thiazolyl 879 —C≡C— 4-thiazolyl 880 —C≡C— 5-thiazolyl 881 —C≡C— 3-pyrazolyl 882 —C≡C— 4-pyrazolyl 883 —C≡C— 1-methyl-3-pyrazolyl 884 —C≡C— 1-methyl-4-pyrazolyl 885 —C≡C— 1-methyl-5-pyrazolyl 886 —C≡C— 2-imidazolyl 887 —C≡C— 1-methyl-2-imidazolyl 888 —C≡C— 5-methyl-[1,3,4]-2-oxadiazolyl 889 —C≡C— 5-methyl-[1,2,4]-3-oxadiazolyl 890 —C≡C— 5-methyl-[1,3,4]-2-thiadiazolyl 891 —C≡C— 5-methyl-[1,2,4]-3-thiadiazolyl 892 —C≡C— [1,2,4]-3-triazolyl 893 —C≡C— [1,2,3]-4-triazolyl 894 —C≡C— 2-pyridyl 895 —C≡C— 6-chloro-2-pyridyl 896 —C≡C— 6-methoxy-2-pyridyl 897 —C≡C— 6-trifluoromethyl-2-pyridyl 898 —C≡C— 3-pyridyl 899 —C≡C— 2-chloro-3-pyridyl 900 —C≡C— 2-methoxy-3-pyridyl 901 —C≡C— 4-pyridyl 902 —C≡C— 2-chloro-4-pyridyl 903 —C≡C— 2-methoxy-4-pyridyl 904 —C≡C— 2-ethoxy-4-pyridyl 905 —C≡C— 2-methylthio-4-pyridyl 906 —C≡C— 2-trifluoromethyl-5-pyridyl 907 —C≡C— 2-pyrimidinyl 908 —C≡C— 3-pyrimidinyl 909 —C≡C— 4-pyrimidinyl 910 —C≡C— 2-pyrazinyl 911 —C≡C— 3-pyridazinyl 912 —C≡C— 4-pyridazinyl 913 —C≡C— 2-(2H-1,3-oxazinyl) 914 —C≡C— 2-(6H-1,3-oxazinyl) 915 —C≡C— 4-(6H-1,3-oxazinyl) 916 —C≡C— 6-(6H-1,3-oxazinyl) 917 —C≡C— [1,3,5]-2-triazinyl 918 —C≡C— [1,2,4]-3-triazinyl 919 —C≡C— [1,2,4]-5-triazinyl 920 —C≡C— [1,2,4]-6-triazinyl

Tables 1-36 below are based on the 2-benzoylcyclohexane-1,3-diones of the formula Ib

Table 1: Compounds 1.1-1.920

Compounds of the formula Ib where R¹ is chlorine, R² is methylsulfonyl, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each hydrogen and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 2: Compounds 2.1-2.920

Compounds of the formula Ib where R¹ and R² are each chlorine, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each hydrogen and where for each individual compounds the substituents X¹ and Het corresponds to one line of Table A.

Table 3: Compounds 3.1-3.920

Compounds of the formula Ib where R¹ is chlorine, R² is trifluoromethyl, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each hydrogen and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 4: Compounds 4.1-4.920

Compounds of the formula Ib where R¹ is methyl, R² is chlorine, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each hydrogen and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 5: Compounds 5.1-5.920

Compounds of the formula Ib where R¹ is methyl, R² is methylsulfonyl, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each hydrogen and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 6: Compounds 6.1-6.920

Compounds of the formula Ib where R¹ is methyl, R² is trifluoromethyl, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are each hydrogen and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 7: Compounds 7.1-7.920

Compounds of the formula Ib where R¹ is chlorine, R² is methylsulfonyl, R⁶, R⁷, R¹⁰ and R¹¹ are each hydrogen, R⁸ and R⁹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 8: Compounds 8.1-8.920

Compounds of the formula Ib where R¹ and R² are each chlorine, R⁶, R⁷, R¹⁰ and R¹¹ are each hydrogen, R⁸ and R⁹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 9: Compounds 9.1-9.920

Compounds of the formula Ib where R¹ is chlorine, R² is trifluoromethyl, R⁶, R⁷, R¹⁰ and R¹¹ are each hydrogen, R⁸ and R⁹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 10: Compounds 10.1-10.920

Compounds of the formula Ib where R¹ is methyl, R² is chlorine, R⁶, R⁷, R¹⁰ and R¹¹ are each hydrogen, R⁸ and R⁹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 11: Compounds 11.1-11.920

Compounds of the formula Ib where R¹ is methyl, R² is methylsulfonyl, R⁶, R⁷, R¹⁰ and R¹¹ are each hydrogen, R⁸ and R⁹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 12: Compounds 12.1-12.920

Compounds of the formula Ib where R¹ is methyl, R² is trifluoromethyl, R⁶, R⁷, R¹⁰ and R¹¹ are each hydrogen, R⁸ and R⁹ is methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 13: Compounds 13.1-13.920

Compounds of the formula Ib where R¹ is chlorine, R² is methylsulfonyl, R⁶, R⁷, R⁸ and R⁹ are each hydrogen, R¹⁰ and R¹¹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 14: Compounds 14.1-14.920

Compounds of the formula Ib where R¹ and R² is chlorine, R⁶, R⁷, R⁸ and R⁹ are each hydrogen, R¹⁰ and R¹¹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 15: Compounds 15.1-15.920

Compounds of the formula Ib where R¹ is chlorine, R² is trifluoromethyl, R⁶, R⁷, R⁸ and R⁹ are each hydrogen, R¹⁰ and R¹¹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 16: Compounds 16.1-16.920

Compounds of the formula Ib where R¹ is methyl, R² is chlorine, R⁶, R⁷, R⁸ and R⁹ are each hydrogen, R¹⁰ and R¹¹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 17: Compounds 17.1-17.920

Compounds of the formula Ib where R¹ is methyl, R² is methylsulfonyl, R⁶, R⁷, R⁸ and R⁹ are each hydrogen, R¹⁰ and R¹¹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 18: Compounds 18.1-18.920

Compounds of the formula Ib where R¹ is methyl, R² is trifluoromethyl, R⁶, R⁷, R⁸ and R⁹ are each hydrogen, R¹⁰ and R¹¹ are each methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 19: Compounds 19.1-19.920

Compounds of the formula Ib where R¹ is chlorine, R² is methylsulfonyl, R⁶, R⁷, R¹⁰ and R¹¹ are each methyl, the CR⁸R⁹ unit forms a group C═O and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 20: Compounds 20.1-20.920

Compounds of the formula Ib where R¹ and R² are each chlorine, R⁶, R⁷, R¹⁰ and R¹¹ are each methyl, the CR⁸R⁹ unit forms a group C═O and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 21: Compounds 21.1-21.920

Compounds of the formula Ib where R¹ is chlorine, R² is trifluoromethyl, R⁶, R⁷, R¹⁰ and R¹¹ are each methyl, the CR⁸R⁹ unit forms a group C═O and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 22: Compounds 22.1-22.920

Compounds of the formula Ib where R¹ is methyl, R² is chlorine, R⁶, R⁷, R¹⁰ and R¹¹ are each methyl, the CR⁸R⁹ unit forms a group C═O and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 23: Compounds 23.1-23.920

Compounds of the formula Ib where R¹ is methyl, R² is methylsulfonyl, R⁶, R⁷, R¹⁰ and R¹¹ are each methyl, the CR⁸R⁹ unit forms a group C═O and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 24: Compounds 24.1-24.920

Compounds of the formula Ib where R¹ is methyl, R² is trifluoromethyl, R⁶, R⁷, R¹⁰ and R¹¹ are each methyl, the CR⁸R⁹ unit forms a group C═O and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 25: Compounds 25.1-25.920

Compounds of the formula Ib where R¹ is methylsulfonyl, R⁶, R⁷, R⁸, R¹⁰ and R¹¹ are each hydrogen, R⁹ is methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 26: Compounds 26.1-26.920

Compounds of the formula Ib where R¹ and R² are each chlorine, R⁶, R⁷, R⁸, R¹⁰ and R¹. are each hydrogen, R⁹ is methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 27: Compounds 27.1-27.920

Compounds of the formula Ib where R¹ is chlorine, R² is trifluoromethyl, R⁶, R⁷, R⁸, R¹⁰ and R¹¹ are each hydrogen, R⁹ is methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 28: Compounds 28.1-28.920

Compounds of the formula Ib where R¹ is methyl, R² is chlorine, R⁶, R⁷, R⁸, R¹⁰ and R¹¹ are each hydrogen, R⁹ is methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 29: Compounds 29.1-29.920

Compounds of the formula Ib where R¹ is methyl, R² is methylsulfonyl, R⁶, R⁷, R⁸, R¹⁰ and R¹¹ are each hydrogen, R⁹ is methyl and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 30: Compounds 30.1-30.920

Compounds of the formula Ib where R¹ is methyl, R² is trifluoromethyl, R⁶, R⁷, R⁸, R¹⁰ and R¹¹ are each hydrogen, R⁹ is methyl and where for each individual compound the substituents XI and Het correspond to one line of Table A.

Table 31: Compounds 31.1-31.920

Compounds of the formula Ib where R¹ is chlorine, R² is methylsulfonyl, R⁶, R⁷, R⁹ and R¹⁰ are each hydrogen, R⁸ and R¹¹ together form a methylene group and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 32: Compounds 32.1-32.920

Compounds of the formula Ib where R¹ and R² are each chlorine, R⁶, R⁷, R⁹ and R¹⁰ are each hydrogen, R⁸ and R¹¹ together form a methylene group and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 33: Compounds 33.1-33.920

Compounds of the formula Ib where R¹ is chlorine, R² is trifluoromethyl, R⁶, R⁷, R⁹ and R¹⁰ are each hydrogen, R⁸ and R¹¹ together form a methylene group and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 34: Compounds 34.1-34.920

Compounds of the formula Ib where R¹ is methyl, R² is chlorine, R⁶, R⁷, R⁹ and R¹⁰ are each hydrogen, R⁸ and R¹¹ together form a methylene group and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 35: Compounds 35.1-35.920

Compounds of the formula Ib where R¹ is methyl, R² is methylsulfonyl, R⁶, R⁷, R⁹ and R¹⁰ are each hydrogen, R⁸ and R¹¹ together form a methylene group and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

Table 36: Compounds 36.1-36.920

Compounds of the formula Ib where R¹ is methyl, R² is trifluoromethyl, R⁶, R⁷, R⁹ and R¹⁰ are each hydrogen, R⁸ and R¹¹ together form a methylene group and where for each individual compound the substituents X¹ and Het correspond to one line of Table A.

The compounds I and their agriculturally useful salts are suitable, both in the form of isomer mixtures and in the form of the pure isomers, as herbicides. The herbicidal compositions comprising I control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leaved weeds and grass weeds in crops such as wheat, rice, maize, soya and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.

Depending on the application method used, the compounds I, or the compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants.

Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I may also be used in crops which tolerate the action of herbicides owing to breeding, including genetic engineering methods.

The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment,. in such a way that they come into contact as little as possible, if at all, with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).

The compounds I, or the herbicidal compositions comprising them, can be used for example in the form of ready-to-spray aqueous solutions, powders, suspensions, including highly concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for broadcasting, or granules, by means of spraying, atomizing, dusting, broadcasting or watering. The application forms depend on the intended uses; in any case, they should guarantee a very fine distribution of the active compounds according to the invention.

Essentially, suitable inert auxiliaries include: mineral oil fractions of medium to high boiling point, such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg. amines such as N-methylpyrrolidone, and water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substituted 2-benzoylcyclohexane-1,3-diones, either as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates comprising active compound, wetting agent, tackifier, dispersant or emulsifier and, if desired, solvent or oil, which are suitable for dilution with water.

Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and also of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active compounds together with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate and ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders, or other solid carriers.

The concentration of the active compounds I in the ready-to-use preparations can be varied within wide ranges. In general, the formulations comprise from 0.001 to 98% by weight, preferably 0.01 to 95% by weight of at least one active compound. The active compounds are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated for example as follows:

I 20 parts by weight of the compound No. 20.39 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide with 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active compound.

II 20 parts by weight of the compound No. 20.39 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide with 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active compound.

III 20 parts by weight of the compound No. 20.39 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280° C. and 10 parts by weight of the adduct of 40 mol of ethylene oxide with 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active compound.

IV 20 parts by weight of the compound No. 20.39 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active compound.

V 3 parts by weight of the compound No. 20.39 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active compound.

VI 20 parts by weight of the compound No. 20.39 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.

VII 1 part by weight of the compound No. 20.39 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.

VIII 1 part by weight of the compound No. 20.39 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (nonionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.

To widen the activity spectrum and to achieve synergistic effects, the substituted 2-benzoylcyclohexane-1,3-diones may be mixed with a large number of representatives of other herbicidal or growth-regulating active compound groups and then applied concomitantly. Suitable components for mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, (het)aryloxyalkanoic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisooxazolidinones, meta-CF₃-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, bipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides and uracils.

It may furthermore be advantageous to apply the compounds I, alone or else concomitantly in combination with other herbicides and/or in the form of a mixture with other crop protection agents, for example together with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.

The active compound application rates are from 0.001 to 3.0, preferably 0.01 to 1.0 kg/ha of active substance (a.s.), depending on the control target, the season, the target plants and the growth stage.

The syntheses of some starting materials and products are described below.

2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone

Step a: Methyl 2-Chloro-3-(2-nitroethenyl)-4-sulfonylmethylbenzoate

With the exclusion of atmospheric moisture, 50 g (0.18 mol) of methyl 2-chloro-3-formyl-4-sulfonylmethylbenzoate, 220 g (3.6 mol) of nitromethane, 216 g (3.6 mol) acetic acid and 7 g (91 mmol) of ammonium acetate are stirred at 85° C. The reaction mixture is poured into 2 l of distilled water and extracted with diethyl ether. The organic phase is washed with saturated aqueous sodium bicarbonate solution, dried with sodium sulfate, filtered and freed from the solvent under reduced pressure. The crude product is recrystallized from n-hexane/ethyl acetate. Yield: 13.1 g, m.p. 147-150° C.

Step b: Methyl 2-Chloro-3-(2-nitroethyl)-4-sulfonylmethylbenzoate

19.4 g (61 mmol) of methyl 2-chloro-3-(2-nitroethenyl)-4-sulfonylmethylbenzoate and 121 g of silica gel 60 are suspended in 180 ml of 2-propanol and 970 ml of chloroform and treated at room temperature with 3.5 g (94 mmol) of sodium borohydride. The reaction mixture is filtered, the filtrate is washed with dichloromethane/methanol 1:1 (v/v) and the organic phase is freed from the solvent under reduced pressure. Yield: 19.5 g; ¹H NMR, δ [ppm], CDCl₃; 3.2 (s), 3.9 (m), 4.0 (s), 4.7 (m), 7.8 (d), 8.1 (d).

Step c: Methyl 2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoate

At room temperature, a solution of 2.8 g (23 mmol) of phenyl isocyanate in 50 ml of toluene is gassed with ethylene. A solution of 3.7 g (11 mmol) of methyl 2-chloro-3-(2-nitroethyl)-4-sulfonylmethylbenzoate and 0.5 ml of triethylamine in 100 ml of toluene is added to this mixture. The reaction mixture is taken up in 300 ml of diethyl ether and the organic phase is extracted with distilled water, and dried with sodium sulfate and filtered and the filtrate is freed from the solvent under reduced pressure. The crude product is purified over silica gel 60 using cyclohexane/ethyl acetate. Yield: 1.0 g; ¹H NMR, δ [ppm], CDCl₃; 3.1 (t), 3.2 (s), 4.0 (s), 4.4 (t), 4.5 (s), 7.7 (d), 8.1 (d).

Step d: 2-Chloro-3-(4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoic Acid

At 5° C., a solution of 2.3 g (7 mmol) of methyl 2-chloro-3-(4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoate in 40 ml of tetrahydrofuran is treated with 0.3 g (13 mmol) of lithium hydroxide. The reaction mixture is taken up in 300 ml of diethyl ether and adjusted to pH 1 using 10% strength aqueous hydrochloric acid. The aqueous phase is extracted with diethyl ether. The combined organic phases are dried over sodium sulfate, filtered and freed from the solvent under reduced pressure. Yield: 1.7 g; ¹H NMR, δ [ppm], DMSO-d₆; 3.0 (t), 3.3 (s), 4.2 (t), 4.3 (s), 7.8 (d), 8.1 (d).

Step e: 2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone (Table 7, Example 39)

At 40° C., a solution of 1.0 g (3 mmol) of 2-chloro-3-(4,5-dihydro-3-isoxazolylmethyl)-4-sulfonylmethylbenzoic acid and 440 mg (3 mmol) of dimedone in 50 ml of acetonitrile is treated with 0.8 g (3.8 mmol) of N,N-dicyclohexylcarbodiimide. After the reaction has ended (monitoring by tlc), 310 mg (3 mmol) of trimethylsilyl cyanide and 950 mg (9 mmol) of triethylamine are added. The reaction mixture is filtered and freed from the solvent under reduced pressure. The crude product is purified over silica gel 60 using toluene/tetrahydrofuran or dichloromethane/toluene. Yield: 600 mg; m.p. 168-173° C.

The compounds described below were prepared in a manner similar to the procedures given above.

2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl(cyclohexane-1,3-dione)methanone (Table 1, Example 39)

m.p. 70-74° C.

2-Chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone (Table 19, Example 39)

40 m.p. 168-173° C.

2,4-Dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)(5,5-dimethylcyclohexane-1,3-dione)methanone (Table 8, Example 39)

m.p. 56-64° C.

2,4-Dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)(3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone (Table 20, Example 39)

m.p. 196-202° C.

2,4-Dichloro-3-((3-(5H-furanone)methyl)phenyl)-(2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione)methanone

Step a: 2,4-Dichloro-3-(3-(5H-furanone)methyl)benzoic Acid

The solution of 13 g (0.038 mol) of tert-butyl 2,4-dichloro-3-(3-furyl)hydroxymethylbenzoate and 1.8 g of p-toluenesulfonic acid in 370 ml of toluene is refluxed for 6 h. The mixture is subsequently poured into 100 ml of 10% strength aqueous sodium hydroxide solution and extracted with ethyl acetate. The aqueous phase is acidified with hydrochloric acid and extracted repeatedly with ethyl acetate. The combined organic phases are washed with water, dried and concentrated. This gives 4.8 g (45%) of the title compound, m.p. 196° C.

Step b: 2,4-Dichloro-3-((3-(5H-furanone)methyl)phenyl)(2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione)methanone

1.6 g (0.0056 mol) of the resulting acid, 1.0 g (0.0056 mol) of 2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione and 1.15 g (0.0056 mol) of dicyclohexylcarbodiimide are stirred in ml of acetonitrile at room temperature. 1.13 g (0.012 mol) of triethylamine and 0.1 ml of trimethylsilyl cyanide are subsequently added, and the mixture is left at room temperature for a further 12 h.

The reaction mixture is diluted with 50 ml of ethyl acetate and mixed with 50 ml of sodium carbonate solution, and the resulting precipitate is discarded. The organic phase is separated off, dried and concentrated.

The resulting residue is chromatographed using a silica gel column (cyclohexane/ethyl acetate 1:10). This gives 120 mg (5%) of the title compound. (Characteristic 13-C NMR data: 209.1, 197.6, 195.9, 195.1, 173.4, 145.6, 137.7, 136.2, 134.7, 131.3, 130.6, 128.6, 126.2, 110.2, 70.5, 27.7.

The following compound was prepared in a similar manner: 2,4-Dichloro-3-((3-(5H-furanone)methyl)phenyl)(1,3-cyclohexanedion-2-yl)methanone

Melting point: 119-121° C.

TABLE 37

¹H m.p. NMR No. R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ Het [° C.] [ppm] 37.1 H H CH₃ CH₃ H H 4,5-dihydro- 64 3-isoxazolyl 37.2 CH₃ CH₃ C═O CH₃ CH₃ 4,5-dihydro- 202 3-isoxazolyl

TABLE 38

¹H m.p. NMR No. R⁶ R⁷ R⁸ R⁹ R¹⁰ R¹¹ Het [° C.] [ppm] 38.1 H H H H H H 4,5-dihydro- 74 3-isoxazolyl 38.2 H H CH₃ CH₃ H H 4,5-dihydro- 96 3-isoxazolyl 38.3 H H CH₃ CH₃ H H 4,5-dihydro- 119 5-methyl-3- isoxazolyl 38.4 H H CH₃ CH₃ H H 3-isoxazolyl 92 38.5 CH₃ CH₃ C═O CH₃ CH₃ 4,5-dihydro- 173 3-isoxazolyl 38.6 CH₃ CH₃ C═O CH₃ CH₃ 4,5-dihydro- 84 5-chloro- methyl-3- isoxazolyl

USE EXAMPLES

The herbicidal activity of the substituted 2-benzoylcyclohexane-1,3-diones of the formula I was demonstrated by greenhouse experiments:

The culture containers used were plastic pots containing loamy sand with approximately 3.0% of humus as the substrate. The seeds of the test plants were sown separately for each species.

For the pre-emergence treatment, the active compounds, which had been emulsified or suspended in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with translucent plastic hoods until the plants had started growing. This cover caused uniform germination of the test plants, unless this was adversely affected by the active compounds.

For the post-emergence treatment, the test plants were first grown to a height of 3 to 15 cm, depending on the plant habit, and only then treated with the active compounds which had been emulsified or suspended in water. The test plants were for this purpose either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. The application rate for the post-emergence treatment was 0.5 or 0.25 kg/ha of a.s.

Depending on the species, the plants were kept at 10-25° C. or 20-35° C. . The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.

The evaluation was carried out using a scale from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage, or normal course of growth.

The plants used in the greenhouse trials were from the following species:

Scientific Name Common Name Chenopodium album lambsquarters (goosefoot) Setaria viridis green foxtail Sinapis alba white mustard Solanum nigrum black nightshade

Herbicidal activity when employed by the post-emergence method (greenhouse)

The compound 37.2, applied post-emergence at application rates of 0.5 or 0.25 kg/ha of a.s., allows very efficient control of the abovementioned weeds. 

We claim:
 1. A 2-benzoylcyclohexane-1,3-dione of the formula I

where: R¹ and R² are each hydrogen, mercapto, nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR³, —OCOR³, —OSO₂R³, —S(O)_(n)R³, —SO₂OR³, —SO₂N(R³)₂, —NR³SO₂R³ or —NR³COR³; R³ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl or phenyl-C₁-C₆-alkyl; where the abovementioned alkyl radicals may be partially or fully halogenated and/or may carry one to three of the following groups: hydroxyl, mercapto, amino, cyano, R³, —OR³, —SR³, —N(R³)₂, ═NOR³, —OCOR³, —SCOR³, —NR³COR³, —CO₂R³, —COSR³, —CON(R³)₂, C₁-C₄-alkyliminooxy, C₁-C₄-alkoxyamino, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxy-C₂-C₆-alkoxycarbonyl, C₁-C₄-alkylsulfonyl, heterocyclyl, heterocyclyloxy, phenyl, benzyl, hetaryl, phenoxy, benzyloxy and hetaryloxy, where the eight last mentioned radicals may in turn be substituted; n is 0, 1 or 2; Q is a cyclohexane-1,3-dione ring with or without substitution which is attached in position 2; X¹ is a straight-chain or branched C₁-C₆-alkylene, a C₂-C₆-alkenylene or a C₂-C₆-alkynylene chain, where the abovementioned alkylene, alkenylene or alkynylene radicals may be partially halogenated and/or may carry one to three of the following groups: —OR⁴, —OCOR⁴, —OCONHR⁴ or —OSO₂R⁴; except for those of the abovementioned alkenylene radicals where the double bond is α,β to the phenyl ring and where Het is linked to the double bond via the β position; R⁴ is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, phenyl, phenyl-C₁-C₆-alkyl, where the abovementioned alkyl, alkenyl or alkynyl radicals may be partially or fully halogenated and/or may be substituted by one or more of the following radicals: hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; Het is a three- to six-membered partially or fully saturated heterocyclic group or a three- to six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of: nitrogen, oxygen and sulfur, where the abovementioned heterocyclic or heteroaromatic group may be partially or fully halogenated and/or may be substituted by R⁵; R⁵ is hydrogen, hydroxyl, mercapto, amino, cyano, nitro, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, where the alkyl radicals may in each case be substituted by in each case one or more of the following radicals: cyano, formyl, C₁-C₄-alkylamino, C₁-C₄-dialkylamino, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylcarbonyloxy, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkylthio, C₁-C₄-haloalkylthio, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy; or an agriculturally useful salt thereof.
 2. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1 in which Q is a cyclohexane-1,3-dione ring of the formula II

which is attached in position 2, where R⁶, R⁷, R⁹ and R¹¹ are each hydrogen or C₁-C₄-alkyl; R⁸ is hydrogen, C₁-C₄-alkyl or C₃-C₄-cycloalkyl, where the two last mentioned groups may carry one to three of the following substituents: halogen, C₁-C₄-alkylthio or C₁-C₄-alkoxy; or is tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where the 6 last mentioned radicals may be substituted by one to three C₁-C₄-alkyl radicals; R¹⁰ is hydrogen, C₁-C₄-alkyl or C₁-C₆-alkoxycarbonyl; or R⁸ and R¹¹ together form a nc bond or a three- to six-membered carbocyclic ring; or the CR⁸R⁹ unit may be replaced by C═O.
 3. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1, in which R¹ is nitro, halogen, cyano, thiocyanato, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkoxy-C₁-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, —OR³ or —S(O)_(n)R³; R² is hydrogen or one of the radicals mentioned above under R¹.
 4. A 2-benzoylcyclohexane-1,3-dione of the formula Ia as claimed in claim 1,

where the substituents R¹, R², Q, X¹ and Het are each as defined in claim
 1. 5. A 2-benzoylcyclohexane-1,3-dione of the formula Ia as claimed in claim 4 where X¹ is a C₁-C₂-alkylene or C₂-alkynylene chain.
 6. A 2-benzoylcyclohexane-1,3-dione of the formula Ia as claimed in claim 1 where Het is a five- or six-membered partially or fully saturated heterocyclic or a five- or six-membered heteroaromatic group having up to three hetero atoms selected from the group consisting of: nitrogen, oxygen and sulfur.
 7. A composition comprising a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione of the formula I or an agriculturally useful salt of I as claimed in claim 1 and auxiliaries which are customarily used for formulating crop protection agents.
 8. A method for controlling undesirable vegetation, which I comprises allowing a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione of the formula I or an agriculturally useful salt of I as claimed in claim 1 to act on plants, their habitat and/or on seeds.
 9. A process for preparing a 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1, which comprises acylating a substituted or unsubstituted cyclohexane-1,3-dione Q with an activated carboxylic acid IIIa or with a carboxylic acid IIIb,

where the substituents R¹, R², X¹ and Het are each as defined in claim 1 and L¹ is a nucleophilically replaceable leaving group and rearranging the acylation product, if appropriate in the presence of a catalyst, to a compound I.
 10. A process for preparing a herbicidally active composition, which comprises mixing a herbicidally effective amount of at least one 2-benzoylcyclohexane-1,3-dione of the formula I or an agriculturally useful salt of I as claimed in claim 1 and auxiliaries which are customarily used for formulating crop protection agents.
 11. An activated carboxylic acid of the formula IIIa and a carboxylic acid of the formula IIIb as defined in claim
 9. 12. A 2-benzoyloyclohexane-1,3-dione of the formula I as claimed in claim 1 in which X¹ is CH₂, CHCH₃, CHOH, CHOCH₃, CHOCOCH₃, CHOSO₂CH₃, CH₂CH₂ or C≡C; Het is selected from the group consisting of oxiranyl, 3-methyl-2-oxiranyl, 2-oxetanyl, 3-hydroxy-3-methyl-2-oxetanyl, 3-hydroxy-3-ethyl-2-oxetanyl, 3-hydroxy-3-propyl-2-oxetanyl, 3-hydroxy-3-butyl-2-oxetanyl, 3-methoxy-3-methyl-2-oxetanyl, 3-methoxy-3-ethyl-2-oxotanyl, 3-methoxy-3-propyl-2-oxetanyl, 3-methoxy-3-butyl-2-oxetanyl, 3-trimethylsilyloxy-3-methyl-2-oxetanyl, 3-trimethylsilyloxy-3-ethyl-2-oxetanyl, 3-oxetanyl, 3-trimethylsilyloxy-3-propyl-2-oxetanyl, 3-trimethylsilyloxy-3-butyl-2-oxetanyl, 3-oxetanyl, 2-furyl, 4,5-dihydro-2-furyl, 2,3-dihydro-2-furyl, 3-furyl, 4,5-dihydro-3-furyl, 2,3-dihydro-3-furyl, 2-thienyl, 4,5-dihydro -2-thienyl, 2,3-dihydro-2-thienyl, 5-chloro-2-thienyl, 5-methyl-2-thienyl, 3-thienyl, 4,5-dihydro-3-thienyl, 2,3-dihydro -3-thienyl, 2-pyrrolyl, 2,5-dihydro-2-pyrrolyl, 3-pyrrolyl, 2,5-dihydro-3-pyrrolyl, 3-isoxazolyl, 4-methyl-3isoxazolyl, 5-methyl-3-isoxazolyl, 4,5-dimethyl-3-isoxazolyl, 4,5-dihydro-3-isoxazolyl, 4-methyl-4,5- dihydro-3- isoxazolyl, 5-methyl-4,5-dihydro-3-isoxazolyl, 4,5-dimethyl-4,5-dihydro-3-isoxazolyl, 4- isoxazolyl, 3-methyl-4-isoxazolyl, 5-methyl-4-isoxazolyl, 5-cyolopropyl-4-isoxazolyl, 5-phenyl-4-isoxazolyl, 3,5-dimethyl-4-isoxazolyl, 4,5-dihydro-4-isoxazolyl, 3-methyl-4,5-dihydro-4-isoxazolyl, 5-methyl-4,5-dihydro-4-isoxazolyl, 3,5-dimethyl-4,5-dihydro-4-isoxazolyl, 5-isoxazolyl, 3-methyl-5-isoxazolyl, 4-methyl-5-isozazolyl, 3,4-dimethyl-5-isoxazolyl, 4,5-dihydro-5-isoxazolyl, 3-methyl-4, 5-dihydro-5-isoxazolyl, 4-methyl-4,5-dihydro-5-isoxazolyl, 3,4-dimethyl-4,5-dihydro-5-isoxazolyl, 3-isothiazolyl, 4-methyl-3-isoxazolyl, 5-methyl-3-isothiazolyl, 4-isothiazolyl, 3-methyl-4-isothiazolyl, 5-methyl-4-isothiazolyl, 5-isothiazolyl, 3-methyl-5-isothiazolyl, 4methyl-5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-pyrazolyl, 4-pyrazolyl, 1-methyl-3-pyrazolyl-1-methyl-4-pyrazolyl-1-methyl-5-pyrazolyl, 2-imidazolyl, 1-methyl-2-imidazolyl, 5-methyl-[1,3,4]-2-oxadiazolyl, 5-methyl-[1,2,4]-3-oxadiazolyl, 5-methyl-[1,3,4]-2-thiaiazolyl, 5-methyl-[1,2,4]-3-thiadiazolyl, [1,2,4]-3-triazolyl, [1,2,3]-4-triazolyl, 2-pyridyl, 6-chloro-2-pyridyl, 6-methoxy-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-pyridyl, 2-chloro-3-pyridyl, 2-methoxy-3-pyridyl, 4-pyridyl, 2-chloro-4-pyridyl, 2-methoxy-4-pyridyl, 2-ethoxy-4-pyridyl, 2-methylthio-4-pyridyl, 2-trifluoromethyl-5-pyridyl, 2-pyrimidinyl, 3-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-(2H-1,3-oxazinyl), 2(6H-1,3-oxazinyl), 4-(6H-1,3-oxazinyl), 6-(6H-1,3-oxazinyl), [1,3,5]-2-triaziayl, [1,2,4]-3-triazinyl, [1,2,4]-5-triazinyl and [1,2,4]-6-triazinyl.
 13. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 2, in which X¹ is CH₂, CHCH₃, CHOH, CHOCH₃, CHOSO₂CH₃, CH₂CH₂ or C≡C; Het is selected from the group consisting of oxiranyl, 3-methyl-2-oxiranyl, 2-oxetanyl, 3-hydroxy-3-methyl-2-oxetanyl, 3-hydroxy-3-ethyl-2-oxetanyl, 3-hydroxy-3-propyl-2-oxetanyl, 3-hydroxy-3-butyl-2-oxetanyl, 3-methoxy-3-methyl-2-oxetanyl, 3-methoxy-3-ethyl-2-oxetanyl, 3-methoxy-3-propyl-2-oxetanyl, 3-methoxy-3-butyl-2-oxetanyl, 3-trimethylsilyloxy-3-methyl-2-oxetanyl, 3-trimethylsilyloxy-3-ethyl-2-oxetanyl, 3-trimethylsilyloxy-3-propyl-2-oxetanyl, 3-trimethylsilyloxy-3-butyl-2-oxetanyl, 3-oxetanyl, 2-furyl, 4,5-dihydro-2-furyl, 2,3-dihydro-2-furyl, 3-furyl, 4,5-dihydro-3-furyl, 2,3-dihydro-3-furyl, 2-thienyl, 4,5-dihydro-2-thienyl, 2,3-dihydro-2-thienyl, 5-chloro-2-thienyl, 5-methyl-2-thienyl, 3-thienyl, 4,5-dihydro-3-thienyl, 2,3-dihydro-3-thienyl, 2-pyrrolyl, 2,5-dihydro-2-pyrrolyl, 3-pyrrolyl, 2,5-dihydro-3-pyrrolyl, 3-isoxazolyl, 4-methyl-3-isoxazolyl, 5-methyl-3-isoxazolyl, 4,5-dimethyl-3-isonzolyl, 4,5-dihydro-3-isoxazolyl, 4-methyl-4,5-dihydro-3-isoxazolyl, 5-methyl-4,5-dihydro-3-isoxazolyl, 4,5-dimethyl-4,5-dihydro-3-isoxazolyl, 4-isoxazolyl, 3-methyl-4-isoxazolyl, 5-methyl-4-isoxazolyl, 5-cyclopropyl-4-isoxazolyl, 5-phenyl-4-isoxasolyl, 3,5-dimethyl-4-isoxazolyl, 4,5-dihydro-4-isoxasolyl, 3-methyl-4,5-dihydro-4-isoxazolyl, 5-methyl-4,5-dihydro-4-isoxazolyl, 3,5-dimethyl-4,5-dihydrol-4-isoxazolyl, 5-isoxazolyl, 3-methyl-5-isoxazolyl, 4-methyl-5-isoxazolyl, 3,4-dimethyl-5-isoxazolyl, 4,5-dihydro-5-isoxazolyl, 3-methyl-4,5-dihydro-5-isoxazolyl, 4-methyl-4,5-dihydro-5-isoxarolyl, 3,4-dimethyl-4,5-dihydro-5-isoxazolyl, 3-isothiazolyl, 4-methyl-3-isothiazolyl, 5-methyl-3-isothiazolyl, 4-isothiatolyl, 3-methyl-4-isothiazolyl, 5-methyl-4-isothiazolyl, 5-isothiazolyl, 3-methyl-5-isothiazolyl, 4-methyl-5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiatolyl, 4-thiatolyl, 5-thiazolyl, 3-pyrazolyl, 4-pyrasolyl, 1-methyl-3-pyrazolyl, 1-methyl-4-pyrazolyl, 1-methyl-5-pyrazolyl, 2-imidazolyl, 1-methyl-2-imidazolyl, 5-methyl-[1,3,4]-2-oxadiazolyl, 5-methyl-[1,2,4]-3-oxadiazolyl, 5-methyl-[1,3,4]-2-thiadiazolyl, 5-methyl-[1,2,4]-3-thiadiazolyl, [1,2,4]-3-triazolyl, [1,2,3]-4-triazolyl, 2-pyridyl, 6-chloro-2-pyridyl-6-methoxy-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 3-pyridyl, 2-chloro-3-pyridyl, 2-methoxy-3-pyridyl-4-pyridyl, 2-chloro-4-pyridyl, 2-methoxy-4-pyridyl, 2-ethoxy-4-pyridyl, 2-methylthio-4-pyridyl, 2-trifluoromethyl-5- pyridyl, 2-pyrimidinyl, 3-pyrimidinyl, 4-pyrimidiayl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-(2H-1,3-oxazinyl), 2-(6H-1,3-oxazinyl), 4-(6H-1,3-oxazinyl), 6-(6H-1,3-oxazinyl), [1,3,5]-2-triazinyl, [1,2,4]-3-triazinyl, [1,2,4]-5-triazinyl and [1,2,4]-6-triazinyl.
 14. A 2-benzoylcyclohexane-1,3-dione of the formula I as claimed in claim 1, which is selected from the group consisting of 2-chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone, 2-chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl(cyclohexane-1,3-dione)methanone, 2-chloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-4-sulfonylmethyl-(3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone, 2,4-dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl)-5,5-dimethylcyclohexane-1,3-dione)methanone, 2,4-dichloro-3-((4,5-dihydro-3-isoxazolylmethyl)phenyl-3,3,6,6-tetramethylcyclohexane-1,3,5-trione)methanone, 2,4-dichloro-3-((3-(5H-furanone)methyl)phenyl)-(2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione)methanone, 2,4-dichloro-3{[3-(5H-furanone)methyl]phenyl}-(1,3-cyclohexanetrione)methanone, 2-chloro-3-[(4,5-dihydro-5-methyl-3-isoxazolylmethyl)phenyl]-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone, 2-chloro-3-[(3-isoxazolylmethyl)phenyl]-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone and 2-chloro-3-[(4,5-dihydro-5-chloromethyl-3-isoxazolylmethyl)phenyl]-4-sulfonylmethyl-(5,5-dimethylcyclohexane-1,3-dione)methanone. 